Fertilizer compositions and methods of making and using the same

ABSTRACT

Generally, the instant disclosure relates to fertilizer compositions and methods of making and using the same. More specifically, the instant disclosure relates to blast suppressant and/or blast resistant ammonium nitrate fertilizer compositions, as well as methods of making and using the same.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application is a continuation of U.S. patent applicationSer. No. 15/479,923 filed Apr. 5, 2017, which is a divisional of U.S.patent application Ser. No. 15/155,319 filed May 16, 2016, which is adivisional of U.S. patent application Ser. No. 14/539,745 filed Nov. 12,2014, now U.S. Pat. No. 9,527,779, which is a non-provisional of andclaims priority to U.S. Patent Application No. 61/903,293 filed Nov. 12,2013, and U.S. Patent Application No. 61/909,625 filed Nov. 27, 2013,all of which are incorporated herein by reference in their entirety.

FIELD OF THE INVENTION

Generally, the instant disclosure relates to fertilizer compositions andmethods of making and using the same. More specifically, the instantdisclosure relates to blast suppressant and/or blast resistant ammoniumnitrate fertilizer compositions, as well as methods of making and usingthe same.

BACKGROUND

Ammonium Nitrate (AN) fertilizer, combined with fuel oil (ANFO) or otherfuels is a common explosive used throughout the world. Unfortunately,due to the availability of ammonium nitrate and fuels (such as fuel oil,powdered sugar, or aluminum powder), malicious parties (e.g. terrorists)are able to obtain these materials and utilize them in explosives (i.e.bombs and improvised explosive devices).

SUMMARY OF THE INVENTION

Various embodiments of the instant disclosure provide for stabilizermaterials to ammonium nitrate fertilizer that reduce, prevent, and/oreliminate the unauthorized use of ammonium nitrate to construct ANFOtype explosives. Broadly, the instant disclosure is directed towards:fertilizer compositions and methods of making the same, in which, due tothe composition, the fertilizer comprises a blast suppression (e.g.measured via specific impulse) and/or desensitization (e.g. measured viaunconfined critical diameter and/or booster quantity needed to initiatedetonation) as compared to existing ammonium nitrate fertilizer(s).

In one aspect, a fertilizer composition is provided, comprising: anammonium nitrate material; and an effective amount of a stabilizermaterial to result in a specific impulse of not greater than 13.5kPa*ms/kg when measured in accordance with a blast propagation test;wherein the stabilizer material comprises a metal (e.g. aluminum)production byproduct wherein the stabilizer material is at least 5 wt. %of the total fertilizer composition.

In some embodiments, the stabilizer material comprises an aluminumproduction byproduct.

In some embodiments, the stabilizer material comprises an additive.

In some embodiments, the fertilizer composition comprises a controlledrelease fertilizer, wherein less than 20 wt. % of the nitrogen contentof the fertilizer is released in a 24 hour period. In some embodiments,the fertilizer comprises a controlled release fertilizer in that notless than 50 wt. % of the nitrogen content of the fertilizer is releasedin a seven day period. In some embodiments, the fertilizer comprises acontrolled release fertilizer in that not less than 80 wt. % of thenitrogen content of the fertilizer is released in a 30 day period.

In another aspect, a fertilizer composition is provided, comprising: anammonium nitrate material; and an effective amount of a stabilizermaterial to result in a specific impulse of not greater than 13.5kPa*ms/kg when measured in accordance with a blast propagation test;wherein the stabilizer material is selected from the group consistingof: BR; LDH; HTC; apatite; bauxite; phosphate compounds; salts oforganic acids; red lime; TCA; aluminum hydroxide; SGA, ESP; andcombinations thereof; wherein the stabilizer material is at least 5 wt.% of the total fertilizer composition.

In yet another aspect, a fertilizer composition is provided, comprising:an ammonium nitrate material; and an effective amount of a stabilizermaterial comprising layered double hydroxide (LDH) material to result ina specific impulse of not greater than 12 kPa*ms/kg when tested inaccordance with a blast propagation test; wherein the LDH material is atleast 10 wt. % of the total fertilizer composition.

In still another aspect, a fertilizer composition is provided,comprising: ammonium nitrate material; and an effective amount of astabilizer material comprising: a layered double hydroxide composition(e.g. HTC) and bauxite residue; to result in a specific impulse of notgreater than 3 kPa*ms/kg when tested in accordance with a blastpropagation test; wherein the combination of LDH and BR comprise notgreater than 25 wt. % of the fertilizer composition.

In another aspect, a fertilizer composition is provided, comprising: anammonium nitrate material; and an effective amount of stabilizermaterial comprising apatite to result in a specific impulse of notgreater than 6 kPa*ms/kg when tested in accordance with a blastpropagation test, wherein the apatite comprises no greater than 25 wt %of the fertilizer composition.

In some embodiments, one or more fertilizer compositions of the instantdisclosure provide for pH adjustment of the soil.

In some embodiments, fertilizer compositions of the instant disclosureprovide for slow release of the fertilizer compounds (as compared to ANfertilizer).

As used herein, “AN-type explosive” means: ammonium nitrate-based fuelexplosives, where fuels include fuel oil (ANFO-type explosives) or otherfuels like powdered sugar or aluminum powder.

As used herein, “fertilizer” means: a substance used to make soil morefertile. In some embodiments of the instant disclosure, a fertilizerincludes ammonium nitrate. In other embodiments, fertilizer is ammoniumnitrate fertilizer which includes at least one stabilizer material,where the stabilizer material is present in a specified amount so as theresulting specific impulse of the fertilizer is not greater than apredetermined threshold, when measured in accordance with a blastpropagation test.

As used herein, “form” means: the shape or structure of something (asdistinguished from its material composition). As some non-limitingexamples, the fertilizer form includes: pellets, prills, granules,powder, and combinations thereof.

In some embodiments, the fertilizer composition of the instantdisclosure is in a single form (i.e. pellets, prills, granules, disks,or powder). In some embodiments, the fertilizer composition of theinstant disclosure is in multiple forms (i.e. a mixture of two or moreforms, including pellets, prills, granules, disks, or powder).

In some embodiments, the fertilizer composition comprises: a mesh sizeof 4, a mesh size of 6, a mesh size of 8, a mesh size of 10, a mesh sizeof 12, a mesh size of 14, a mesh size of 16, a mesh size of 18, or amesh size of 20.

In some embodiments, the fertilizer composition comprises: a mesh sizeof 20, a mesh size of 30, a mesh size of 40, a mesh size of 50, a meshsize of 60, a mesh size of 70, a mesh size of 80, a mesh size of 90, ora mesh size of 100.

As used herein, “prill” means: a pellet formed by generating dropletsallowing the drops to solidify. In some embodiments, the stabilizermaterial(s) is/are added ammonium nitrate prior to prilling. In someembodiments, the stabilizer material (s) is/are added to ammoniumnitrate after prilling (i.e. co-prilling or coating after the AN productis prilled).

In some embodiments, the mesh size of a prill product is between 4 and20 mesh (i.e. ˜4700 microns-˜830 microns).

As used herein, “pellet” means a rounded body (e.g. spherical,cylindrical). In some embodiments, the ammonium nitrate and stabilizermaterial (s) are ground (e.g. milled), mixed, and then pelletizedtogether to form a pellet containing both AN and stabilizer material (s)therein at a desired weight percentage. In some embodiments, the meshsize of a pellet product is between 4 and 20 mesh.

As used herein, “powder” means: matter in a finely divided state. Insome embodiments, the ammonium nitrate and stabilizer material (s) areground (either independently or in combination) to yield a powderproduct having a particular average particle size. In some embodiments,the mesh size of a powder product is greater than 20 mesh.

As used herein, “granule” means: a small particle. In some embodiments,the ammonium nitrate is crushed (i.e. reduced in size from prilled orpellet form) into smaller pieces (which are particulate in form asopposed to powder). In some embodiments, the ammonium nitrate iscombined with the stabilizer material(s) during the ammonium nitrateproduction process to form a composition having both ammonium nitrateand stabilizer material(s) therein. In some embodiments, the mesh sizeof a granule product is between 4 and 20 mesh.

In some embodiments, the fertilizer composition comprises a homogenousmixture.

In some embodiments, the fertilizer composition comprises aheterogeneous mixture.

In some embodiments, the fertilizer compositions include: uncoatedmaterials, coated materials, and/or multi-coated materials (i.e. morethan one coating).

Generally, addition of a stabilizer material in accordance with theinstant disclosure causes blast suppression and/or a desensitization ofthe resulting fertilizer composition.

As used herein, “blast suppression” means: the reduction of a materialstendency to explode (as measured by specific impulse).

As used herein, “blast suppression test” means a test to measure thequantity and/or quality of blast suppression of an underlying stabilizermaterial present in a fertilizer composition for a given mesh size (e.g.20, 40, or 60 mesh). In some embodiments, blast suppression test means atest article set atop a witness plate, where the test article houses afertilizer composition (which includes the stabilizer material) and adetonator (C4 booster) placed adjacent to the top end of the testarticle. In some embodiments, overpressure sensors positioned a setdistance from the test article are used to quantify the specific impulseof the blast. In some embodiments, the witness plate is used to obtainqualitative data from the blast (perforation means a detonation offertilizer composition occurred, non-perforation means no detonation ofthe fertilizer composition occurred). In some embodiments, variableslike test article diameter, booster quantity, and fuel oil quantity areused to obtain desensitization measurements (i.e. an increase indiameter of the test article to account for an increase in unconfinedcritical diameter, an increase in booster quantity required to detonatethe fertilizer composition, an increase in fuel oil in the fertilizercomposition, and/or combinations thereof)

As used herein, “pressure impulse” refers to the amount of pressuremeasured during a detonation of an explosive (e.g. measured in Pa*ms).In some embodiments, impulse pressure (sometimes called detonationpressure) is measured with overpressure sensors.

As used herein, “specific impulse” means: an amount of force a materialhas per unit of time with respect to an amount of explosive used (e.g.measured in units of kPa*ms/kg). For example, the higher the impulse,the greater the blast/detonation of the blast media (e.g. fertilizer asmeasured at a distance of 7 m).

In some embodiments, specific impulse is utilized as a variable toexpress the characteristic of blast suppression (i.e. reduction,prevention, or elimination of a material's tendency to detonate/explode)for stabilizer materials in accordance with the various embodiments ofthe instant disclosure.

In some embodiments, the specific impulse of a fertilizer composition inaccordance with the embodiments of the instant disclosure is less thanthe specific impulse of an ammonium nitrate fertilizer (e.g. wherecommercially available fertilizer has an ammonium nitrate content ofabout 98-100% AN).

Specific Impulse is calculated via the following formula:

Specific impulse=((Impulse_(Total)−Impulse_(Booster))/(1−Conc.))/ChargeMass

where Impulse_(Total) is the average measure of the pressure sensors(overpressure sensors), which is corrected for: (a) the booster (i.e.Impulse_(Booster)), (b) the mass of the charge (measured value), and (c)the % dilution (measured value).

In some embodiments (e.g. with reference to the blast tests completed inthe Examples sections), as the blast components were prepared, there issome level of variability in the specific impulse values obtained forthe “same” materials. Without being bound by a particular mechanism ortheory, non-limiting examples of possible sources of error or variationinclude: variability in the packing of the materials, environment oftesting, time of day of blast, mixing of the material, humidity, cloudcover, makeup of the fertilizer itself, and combinations thereof.

For example, without being bound by a particular mechanism or theory,variability in packing of the materials is believed to potentiallyresult in varying amount of voids in different samples for the samematerial, which can result in different specific impulse values for thesame materials (e.g. resulting in experimental error and/or outliers).

In some embodiments, the specific impulse of a composition of theinstant disclosure is: less than 13.5 kPa*ms/kg; less than 13 kPa*ms/kg;less than 12.5 kPa*ms/kg; less than 12 kPa*ms/kg; less than 11.5kPa*ms/kg; less than 11 kPa*ms/kg; less than 10.5 kPa*ms/kg; less than10 kPa*ms/kg; less than 9.5 kPa*ms/kg; less than 9 kPa*ms/kg; less than8.5 kPa*ms/kg; less than 8 kPa*ms/kg; less than 7.5 kPa*ms/kg; less than7 kPa*ms/kg; less than 6.5 kPa*ms/kg; less than 6 kPa*ms/kg; less than5.5 kPa*ms/kg; less than 5 kPa*ms/kg; less than 4.5 kPa*ms/kg; less than4 kPa*ms/kg; less than 3.5 kPa*ms/kg; less than 3 kPa*ms/kg; less than2.5 kPa*ms/kg; less than 2 kPa*ms/kg; less than 1.5 kPa*ms/kg; or lessthan 1 kPa*ms/kg.

In some embodiments, the specific impulse of a composition of theinstant disclosure is: less than 1 kPa*ms/kg; less than 0.8 kPa*ms/kg;less than 0.6 kPa*ms/kg; less than 0.5 kPa*ms/kg; less than 0.4kPa*ms/kg; less than 0.2 kPa*ms/kg; less than 0.1 kPa*ms/kg; less than0.05 kPa*ms/kg; or less than 0.01 kPa*ms/kg.

In some embodiments, the specific impulse of a composition of theinstant disclosure is: not greater than 13.5 kPa*ms/kg; not greater than13 kPa*ms/kg; not greater than 12.5 kPa*ms/kg; not greater than 12kPa*ms/kg; not greater than 11.5 kPa*ms/kg; not greater than 11kPa*ms/kg; not greater than 10.5 kPa*ms/kg; not greater than 10kPa*ms/kg; not greater than 9.5 kPa*ms/kg; not greater than 9 kPa*ms/kg;not greater than 8.5 kPa*ms/kg; not greater than 8 kPa*ms/kg; notgreater than 7.5 kPa*ms/kg; not greater than 7 kPa*ms/kg; not greaterthan 6.5 kPa*ms/kg; not greater than 6 kPa*ms/kg; not greater than 5.5kPa*ms/kg; not greater than 5 kPa*ms/kg; not greater than 4.5 kPa*ms/kg;not greater than 4 kPa*ms/kg; not greater than 3.5 kPa*ms/kg; notgreater than 3 kPa*ms/kg; not greater than 2.5 kPa*ms/kg; not greaterthan 2 kPa*ms/kg; not greater than 1.5 kPa*ms/kg; or not greater than 1kPa*ms/kg.

In some embodiments, the specific impulse of a composition of theinstant disclosure is: not greater than 1 kPa*ms/kg; not greater than0.8 kPa*ms/kg; not greater than 0.6 kPa*ms/kg; not greater than 0.5kPa*ms/kg; not greater than 0.4 kPa*ms/kg; not greater than 0.2kPa*ms/kg; not greater than 0.1 kPa*ms/kg; not greater than 0.05kPa*ms/kg; or not greater than 0.01 kPa*ms/kg.

In some embodiments, a fertilizer composition in accordance with theinstant disclosure comprises a specific impulse reduction of: at least a10% reduction in specific impulse; at least a 15% reduction in specificimpulse; at least a 20% reduction in specific impulse; at least a 25%reduction in specific impulse; at least a 30% reduction in specificimpulse; at least a 35% reduction in specific impulse; at least a 40%reduction in specific impulse; at least a 45% reduction in specificimpulse; at least a 50% reduction in specific impulse; at least a 55%reduction in specific impulse; at least a 60% reduction in specificimpulse; at least a 65% reduction in specific impulse; at least a 70%reduction in specific impulse; at least a 75% reduction in specificimpulse; at least a 80% reduction in specific impulse; at least a 85%reduction in specific impulse; at least a 90% reduction in specificimpulse; or at least a 95% reduction in specific impulse, when comparedto the specific impulse of a commercially available ammonium nitratefertilizer composition.

In some embodiments, a fertilizer composition in accordance with theinstant disclosure comprises a specific impulse reduction of: at least a90% reduction in specific impulse; at least a 92% reduction in specificimpulse; at least a 95% reduction in specific impulse; at least a 97%reduction in specific impulse; at least a 98% reduction in specificimpulse; at least a 99% reduction in specific impulse; or at least a99.3% reduction in specific impulse, when compared to the specificimpulse of a commercially available ammonium nitrate fertilizercomposition.

In some embodiments, a fertilizer composition in accordance with theinstant disclosure comprises: not greater than a 10% reduction inspecific impulse; not greater than a 15% reduction in specific impulse;not greater than a 20% reduction in specific impulse; not greater than a25% reduction in specific impulse; not greater than a 30% reduction inspecific impulse; not greater than a 35% reduction in specific impulse;not greater than a 40% reduction in specific impulse; not greater than a45% reduction in specific impulse; not greater than a 50% reduction inspecific impulse; not greater than a 55% reduction in specific impulse;not greater than a 60% reduction in specific impulse; not greater than a65% reduction in specific impulse; not greater than a 70% reduction inspecific impulse; not greater than a 75% reduction in specific impulse;not greater than a 80% reduction in specific impulse; not greater than a85% reduction in specific impulse; not greater than a 90% reduction inspecific impulse; not greater than a 95% reduction in specific impulseas compared to a commercially available ammonium nitrate fertilizercomposition.

In some embodiments, a fertilizer composition in accordance with theinstant disclosure comprises a reduction in specific impulse of: notgreater than a 90% reduction in specific impulse; not greater than a 92%reduction in specific impulse; not greater than a 95% reduction inspecific impulse; not greater than a 97% reduction in specific impulse;not greater than a 98% reduction in specific impulse; not greater than a99% reduction in specific impulse; not greater than a 99.3% reduction inspecific impulse, when compared to the specific impulse of acommercially available ammonium nitrate fertilizer.

As used herein, “desensitization” means: the reduction in the criticalenergy of detonation of a material. As a non-limiting example,desensitization results in a material's reduced ability or inability toexplode, when given a donor charge (i.e. booster) or when impacted froma fragment. In some embodiments, desensitization is characterized viaunconfined critical diameter of the fertilizer composition. In someembodiments, desensitization is quantified by the booster quantityneeded to cause an explosion (i.e. or a non-explosive event at a largequantity of booster size).

As used herein, “unconfined critical diameter” means a minimum diameterthat a given volume of explosive material must be in, in order tosustain a detonation front (i.e. explode). In some embodiments,unconfined critical diameter is a variable which is used to measurewhether a particular stabilizer material or combination of stabilizermaterials have the ability to desensitize an ANFO-type material fromdetonating/exploding.

In some embodiments, when compared to AN fertilizers, fertilizercompositions of the instant disclosure are “desensitized” by: at least afactor of two; at least a factor of three; at least a factor of four; atleast a factor of five; at least a factor of six; at least a factor ofseven; at least a factor of eight; at least a factor of nine; or atleast a factor of ten.

In some embodiments, when compared to AN fertilizers, fertilizercompositions of the instant disclosure are “desensitized” by: notgreater than a factor of two; not greater than a factor of three; notgreater than a factor of four; not greater than a factor of five; notgreater than a factor of six; not greater than a factor of seven; notgreater than a factor of eight; not greater than a factor of nine; ornot greater than a factor of ten.

As a non-limiting example, in some embodiments, the fertilizercomposition increased the unconfined critical diameter (CD) from fiveinches (for ANFO) to six inches, seven inches, or eight inches.

As used herein, “detonation” means a supersonic exothermic frontaccelerating through a medium that eventually drives a shock frontpropagating from it (i.e. directly in front of it).

In some embodiments, the metrics of blast suppression and/ordesensitization are measured qualitatively, by visual observation of awitness plate after a test article undergoes blast testing. If thewitness plate (i.e. steel plate) is perforated, it indicates thatdetonation occurred (i.e. both C4 booster charge and the testmedia—fertilizer composition with fuel oil detonated). If the witnessplate is not perforated (including bent plate), it indicates that onlythe booster charge exploded and the blast did not detonate themedia—fertilizer composition in fuel oil.

As used herein, “ammonium nitrate material” (also interchangeablyreferred to as AN) means: a composition including ammonium nitrate(NH₄NO₃). In some embodiments, ammonium nitrate is used in agricultureas a high-nitrogen fertilizer, though AN fertilizer can also be used asan oxidizing agent in explosives (e.g. including improved explosivedevices).

As used herein, “stabilizer material” means: a material added to anothermaterial to prevent or retard an unwanted alteration of physical state.In some embodiments, a stabilizer material is present with an ammoniumnitrate material to provide a fertilizer composition which prevents orretards an unwanted oxidation/explosion of the composition. In someembodiments, the stabilizer material comprises an additive.

As used herein, “additive” means: a substance added to another indefined amounts to effect a desired change in one or more properties. Inaccordance with the instant disclosure, an additive is added to afertilizer comprising ammonium nitrate in order to prevent, reduce, oreliminate the ability of the composition to be utilized as a material(e.g. oxidizing material) in an explosive and/or explosive device.

In some embodiments, the presence of a stabilizer material in thefertilizer composition (i.e. at a particular wt. %) prevents thecomposition from exploding (i.e. when measured in accordance with ablast propagation test). In other embodiments, the presence of astabilizer material in the fertilizer composition (i.e. at a particularwt. %) reduces the specific impulse of the composition.

In some embodiments, the fertilizer composition comprises: at least 5wt. % stabilizer material; at least 7 wt. % stabilizer material; atleast 10 wt. % of stabilizer material; at least 15 wt. % of stabilizermaterial; at least 20 wt. % of stabilizer material; at least 25 wt. % ofstabilizer material; at least 30 wt. % of stabilizer material; at least35 wt. % of stabilizer material; at least 40 wt. % of stabilizermaterial; at least 45 wt. % of stabilizer material; or at least 50 wt. %of stabilizer material.

In some embodiments, the fertilizer composition comprises: not greaterthan 5 wt. % of stabilizer material; not greater than 7 wt. % ofstabilizer material; not greater than 10 wt. % of stabilizer material;not greater than 15 wt. % of stabilizer material; not greater than 20wt. % of stabilizer material; not greater than 25 wt. % of stabilizermaterial; not greater than 30 wt. % of stabilizer material; not greaterthan 35 wt. % of stabilizer material; not greater than 40 wt. % ofstabilizer material; not greater than 45 wt. % of stabilizer material;or not greater than 50 wt. % of stabilizer material.

As used herein, “explosive device” means: a device that provides for asudden, loud, and violent release of energy that happens when the device(or material therein) breaks apart in such a way that sends parts flyingoutward. Non-limiting examples of explosive devices include bombs and/orimprovised explosive devices.

As used herein, “booster” means: an auxiliary device for increasingforce, power, pressure, or effectiveness. In some embodiments, boosterrefers to the portion of the blast propagation test that initializes theblast. In some embodiments, the booster in the blast propagation testincludes C4 explosive.

As used herein, “detonation” means: the act or process of exploding ofcausing something to explode. In some embodiments, one or morestabilizer materials of the instant disclosure effect a reduction in orelimination of the detonation of ammonium nitrate material (e.g.utilized in an explosive device as an oxidizing material).

As used herein, “suppressant” means: an agent that tends to prevent,control, or reduce the intensity of a particular property of a material.In some embodiments, suppressant effects are quantified by measuring areduction in specific impulse of a fertilizer composition, as comparedto control (commercially available AN or AN fertilizer) or existingblast resistant fertilizers (e.g. CAN-27). In some embodiments,suppressant refers to a chemical mechanism of blast inhibition and/orprevention.

As used herein, “diluent” means: a diluting agent. In some embodiments,the stabilizer materials to the ammonium nitrate act as filler, thinningout the proximity of particles of ammonium nitrate from one another. Insome embodiments, diluent refers to a mechanical mechanism of blastinhibition and/or prevention (i.e. dilution by addition of stabilizermaterial which acts as a filler material).

As used herein, “substantially non-reactive” means: dimensionallystable. In some embodiments, substantially non-reactive means inert(non-reacting). Some non-limiting examples of substantially non-reactivestabilizer materials include: sand, clay (i.e. naturally occurringand/or synthetic clays), aggregate (i.e. rocks), and the like.

As used herein, “byproduct of metal production” means: a compound orclass of materials that is produced by one or more processes of makingnon-ferrous metal (e.g. aluminum). Some non-limiting processes include:the Bayer process, smelting, refining, casting, recycling, producingvarious products, product forms, and combinations thereof.

Some non-limiting examples of stabilizer materials that are products ofaluminum production and/or processing include: apatite, electrostaticprecipitator fines (ESP), Bayer process byproducts, and combinationsthereof.

As used herein, “Bayer process byproduct” means: a substance producedduring the reduction of bauxite to form/produce alumina. Non-limitingexamples of stabilizer materials that are Bayer process byproductsinclude: layered double hydroxides, hydrotalcite, bauxite residue,neutralized bauxite residue, dawsonite, fukalite, aluminum hydroxide,smelter grade alumina (SGA), and combinations thereof.

As used herein, “layered double hydroxide” means: a class of compoundswhich are characterized by multiple (e.g. two) positively charged layersand weakly bound, often exchangeable central ion(s) (e.g. negativelycharged ions) located in the interlayer (middle) region. As anon-limiting example, LDHs are commonly referred to by the followinggeneric chemical formula:

[M²⁺ _(1-x)M³⁺(OH)₂]^(q+)(X^(n−))_(q/n−) *yH₂O  (eq. 1)

As some non-limiting examples, z=2, M²⁺=Ca, Mg²⁺, Mn²⁺, Fe²⁺, Co²⁺,Ni²⁺, Cu²⁺, or Zn²⁺, (hence q=x).

Non-limiting examples of LDH compounds include: hydrotalcites,hydrocalumite, hydromagnesite, takovite, woolite, and combinationsthereof.

In some embodiments, “unavoidable minor components” means: variouschemicals and minerals that are present in the stabilizer materials.Some non-limiting examples include: iron-containing compounds (e.g.Fe₂O₃; FeOOH; Fe₃O₄₎; silicon-containing compounds (e.g. SiO₂);titanium-containing compounds (e.g. TiO₂); sodium-containing compounds(e.g. NaOH; NaNO₃; Na₃PO₄; Na₂HPO₄; Na₂CO₃); calcium-containingcompounds (e.g. CaO; Ca(OH)₂; CaSO₄; CaCO₃; Ca₃(Al(OH)₄)₆; TCA(tricalcium aluminate)); magnesium-containing compounds (e.g. MgO;Mg(OH)₂; MgCO₃); anionic organic compounds (e.g. oxalate (sodiumoxalate), formate (ammonia formate), acetate); aluminum-containingcompounds (e.g. Al(OH)₃; AlOOH); and combinations thereof.

In some embodiments, the total weight percent of unavoidable minorcomponents is not greater than 30 wt. % (i.e. for each compound). Insome embodiments, the unavoidable minor component is: not greater than30 wt. %; not greater than 25 wt. %; not greater than 20 wt. %; notgreater than 15 wt. %; not greater than 10 wt. %; not greater than 7 wt.%; not greater than 5 wt. %; not greater than 3 wt. %; not greater than1%; not greater than 0.5 wt. %; not greater than about 0.3 wt. %; or notgreater than 0.1 wt. %.

In some embodiments, the unavoidable minor component is: not less than30 wt. %; not less than 25 wt. %; not less than 20 wt. %; not less than15 wt. %; not less than 10 wt. %; not less than 7 wt. %; not less than 5wt. %; not less than 3 wt. %; not less than 1%; not less than 0.5 wt. %;or not less than about 0.1 wt. %.

In some embodiments, for bauxite residue the unavoidable minor componentcontent are not greater than 30 wt. % for each component.

In some embodiments, for bauxite, the content of unavoidable minorcomponents is not greater than 30 wt. % for each component.

In some embodiments, for HTC, the content of unavoidable minorcomponents is not greater than 20 wt. % for each component.

In some embodiments, for apatite, the content of unavoidable minorcomponents is not greater than 20 wt. % for each component.

In some embodiments, for smelting grade alumina, the content ofunavoidable minor components is not greater than about 1 wt. %.

As used herein, “intercalated” means: a substances which has anothersubstance or material inserted between or among existing elements orlayers. In some embodiments, an LDH is intercalated with itscentral/interlayer region being replaced with other anions or compounds.

Non-limiting examples of intercalated LDH (sometimes called iLDH)include: herbicides, pesticides, anti-fungal agents, supplementalnutrients (e.g. phosphorous compounds, nitrogen compounds, sulfurcompounds, trace-element compounds, and combinations thereof). In someembodiments, the LDH is intercalated with a nitrate. In someembodiments, the LDH is intercalated with a sulfate. In someembodiments, the LDH is intercalated with a phosphate.

In some embodiments, LDH comprises hydrotalcite (HTC). In someembodiments, LDH comprises hydrocalumite.

As used herein, “hydrotalcite” means: a layered double hydroxide of thefollowing formula:

Mg₆Al₂(CO₃)(OH)₁₆*4(H₂O)  (eq. 2)

Non-limiting examples of groups of materials within the hydrotalcitessupergroup include: hydrotalcites group, quintinite group, fougeritegroup, woodwardite group, glaucerinite group, cualstibite group,hydrocalumite group, and unclassified.

Non-limiting examples of hydrotalcites include: pyroaurite, stichtite,meixnerite, iowaite, droninoite, woodallite, desaurelsite, takovite,reevesite, jamborite, quintinite, charmarite, caresite, zaccagnaite,chrlomagaluminite, fougerite, woodwardite, zincowoodwardite, honessite,claucocerinite, hydrowoodwardite, carrboydite, hydrohonessite,mountkeithite, sincaluminite, wermlandite, shigaite, nikischerite,motukoreaite, natroglaucocerinite, karchevskyite, cualstibite,xincalstibite, hydroclumite, kuzelite, coalingite, brugnatellite,muskoxite, and combinations thereof.

Non-limiting examples of intercalated hydrotalcites (sometimes callediHTC) include: HTC-carbonate, HTC-phosphate, HTC-nitrate, andcombinations thereof.

As used herein, “apatite” means: a phosphate mineral having calciumphosphate with some fluorine, chlorine, and other elements. In someembodiments, apatite is neutralized with group of phosphate minerals.One example of an apatite compound is hydroxyapatite.

As used herein, “bauxite residue” means: particulate alkaline clayproduced as a byproduct of the Bayer Process (e.g. the process ofrefining of bauxite ore into alumina). In some embodiments, bauxiteresidue (sometimes called red mud) includes a plurality of metals, metaloxides, clay, and zeolites. In some embodiments, the bauxite residue isgenerally free from draining liquids and is neutralized from itsoriginal form (i.e. slurry having volatile components at a pH ofapproximately 13).

In some embodiments, bauxite residue may be neutralized via acid orneutralized by the atmosphere (e.g. via reaction with ambient carbondioxide and/or contact with anthropogenic carbon dioxide).

In some embodiments, the BR is neutralized with aluminum hydroxide,forming bauxite residue (NO₃). In some embodiments, the resulting BRcompound has a nitrate content of 5-10 wt. %.

In some embodiments, the BR is neutralized with phosphoric acid, formingbauxite residue (PO₄). In some embodiments, the resulting BR compoundhas a phosphate content of 5-10 wt. %.

As used herein, “acid neutralized” means: a material which is madechemically neutral (or closer to neutral) through the addition of anacid. Non-limiting acids include: phosphoric acid, nitric acid, sulfuricacid, organic acids, minerals, and combinations thereof.

As used herein, “dawsonite” means: a sodium aluminate carbonatehydroxide compound. In some embodiments, dawsonite is a byproduct of therefining step(s) (e.g. after addition of sodium hydroxide in the BayerProcess).

As used herein, “fukalite” means: a calcium silicate carbonate compound.In some embodiments, fukalite is a hydroxide or a fluoride derivative ofa calcium silicate carbonate compound. In some embodiments, fukalite isa byproduct of the refining step(s) (e.g. after addition of sodiumhydroxide in the Bayer Process).

In some embodiments, dawsonite, fukalite, hydroxyapatite, andhydroxymagnesite are components in bauxite residue. In some embodiments,dawsonite, fukalite, hydroxyapatite, and hydroxymagnesite are componentsin bauxite.

As used herein, “ESP” means the dust that comes from an electrostaticprecipitator (i.e. used to clean industrial process exhaust streams). Insome embodiments, ESP comprises (e.g. as a major component) aluminafines which are removed from exhaust fumes of industrial processes.

As used herein, “bauxite” means: an ore from which alumina is extracted.In some embodiments, bauxite ore comprises: alumina, iron oxides,silicates, calcium carbonate, sodium hydroxide, calcium oxide, titania,manganese oxide, magnesium oxide, phosphates. In some embodiments,bauxite comprises at least 30 wt. % alumina; at least 40% alumina; atleast 50% alumina; at least 60% alumina; at least 70 wt. %; at least 80wt. %; at least 90 wt. %, or higher.

In some embodiments, phosphogypsum is used to neutralize bauxiteresidue.

As used herein, “hydromagnesite” means: a magnesium carbonate mineral.

As used herein, “dolomite” means an ore having magnesium carbonate andcalcium carbonate therein.

As used herein, “red lime” means: a mixture of tricalcium aluminate(TCA) and calcium carbonate, with some iron oxides present, which is abyproduct of aluminum processing.

In some embodiments, TCA is the major component (i.e. at least 51 wt. %)in red lime. In some embodiments, TCA is: at least 50 wt. %: at least 55wt. %; at least 60 wt. %; at least 65 wt. %; at least 70 wt. %; at least75 wt. %; at least wt. 80%; at least 85 wt. %; at least 90 wt. %; atleast 95 wt. %; or at least 99 wt. % (with the remainder being calciumcarbonate and/or iron oxides).

In some embodiments, TCA is the major component (i.e. not greater than51 wt. %). In some embodiments, TCA is: not greater than 50 wt. %: notgreater than 55 wt. %; not greater than 60 wt. %; not greater than 65wt. %; not greater than 70 wt. %; not greater than 75 wt. %; not greaterthan. 80 wt %; not greater than 85 wt. %; not greater than 90 wt. %; notgreater than 95 wt. %; or not greater than 99 wt. % (with the remainderbeing calcium carbonate and/or iron oxides).

As used herein, “binder” means: a material that is used to hold thingstogether. As some non-limiting examples, embodiments of binders include:waste from paper mills, sugars, polymers, starches, water, guar gum,clays (e.g. bentonite), sodium silicates, and combinations thereof.

In one embodiment, the fertilizer composition stabilizer material is: BR(acid neutralized, anthropogenically neutralized, or phosphogypsumneutralized); LDH (as-is or intercalated); HTC (as-is or intercalated);apatite; bauxite; phosphate compounds (e.g. potassium phosphate, calciumphosphate, sodium phosphate, diammonium phosphate), salts of organicacids (e.g. oxalate, formate, acetate), red lime, TCA, aluminumhydroxide (also called hydrate), SGA, ESP, and inert agents (e.g. sand,clay).

In one embodiment, when the fertilizer composition has 10 wt. % ofstabilizer material and there are two stabilizer materials present (afirst and a second), the content of first to second stabilizer materialsare as follows: 2 wt. % of a first and 8 wt. % of a second or 5 wt. % ofeach of the first and the second.

In one embodiment, when the fertilizer composition has 15 wt. % ofstabilizer material and there are two stabilizer materials present (afirst and a second), the content of first to second stabilizer materialsare as follows: 5 wt. % of a first and 10 wt. % of a second, 7.5 wt. %of each of the first and the second.

In one embodiment, when the fertilizer composition has 20 wt. % ofstabilizer material and there are two stabilizer materials present (afirst and a second), the content of first to second stabilizer materialsare as follows: 5 wt. % of a first and 15 wt. % of a second, or 10 wt. %of each of the first and the second.

In one embodiment, when the fertilizer composition has 25 wt. % ofstabilizer material and there are two stabilizer materials present (afirst and a second), the content of first to second stabilizer materialsare as follows: 5 wt. % of a first and 20 wt. % of a second, 10 wt. % ofa first and 15 wt. % of a second; 12.5 wt % of each of the first and thesecond.

In one embodiment, when the fertilizer composition has 30 wt. % ofstabilizer material and there are two stabilizer materials present (afirst and a second), the content of first to second stabilizer materialsare as follows: 5 wt. % of a first and 25 wt. % of a second, 10 wt. % ofa first and 20 wt. % of a second; 15 wt. % of each of a first andsecond.

In one embodiment, the fertilizer composition stabilizer material is:BR; LDH; HTC; apatite; bauxite; phosphate compounds; salts of organicacids; red lime; TCA; aluminum hydroxide; SGA, ESP, and inert agents(e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is: BRand LDH. In one embodiment, the fertilizer composition stabilizermaterial is: BR and HTC. In one embodiment, the fertilizer compositionstabilizer material is: BR and apatite. In one embodiment, thefertilizer composition stabilizer material is: BR and bauxite. In oneembodiment, the fertilizer composition stabilizer material is: BR andphosphate compounds. In one embodiment, the fertilizer compositionstabilizer material is: BR and salts of organic acids. In oneembodiment, the fertilizer composition stabilizer material is: BR andred lime. In one embodiment, the fertilizer composition stabilizermaterial is: BR and TCA. In one embodiment, the fertilizer compositionstabilizer material is: BR and aluminum hydroxide. In one embodiment,the fertilizer composition stabilizer material is: BR and SGA. In oneembodiment, the fertilizer composition stabilizer material is: BR andESP. In one embodiment, the fertilizer composition stabilizer materialis: BR and inert agents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:LDH (other than HTC) and HTC. In one embodiment, the fertilizercomposition stabilizer material is: LDH and apatite. In one embodiment,the fertilizer composition stabilizer material is: LDH and phosphatecompounds. In one embodiment, the fertilizer composition stabilizermaterial is: LDH and salts of organic acids. In one embodiment, thefertilizer composition stabilizer material is: LDH and red lime. In oneembodiment, the fertilizer composition stabilizer material is: LDH andTCA. In one embodiment, the fertilizer composition stabilizer materialis: LDH and aluminum hydroxide. In one embodiment, the fertilizercomposition stabilizer material is: LDH and SGA. In one embodiment, thefertilizer composition stabilizer material is: LDH and ESP. In oneembodiment, the fertilizer composition stabilizer material is: LDH andinert agents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:HTC and apatite. In one embodiment, the fertilizer compositionstabilizer material is: HTC and bauxite. In one embodiment, thefertilizer composition stabilizer material is: HTC and phosphatecompound. In one embodiment, the fertilizer composition stabilizermaterial is: HTC and salts of organic acids. In one embodiment, thefertilizer composition stabilizer material is: HTC and red lime. In oneembodiment, the fertilizer composition stabilizer material is: HTC andTCA. In one embodiment, the fertilizer composition stabilizer materialis: HTC and aluminum hydroxide. In one embodiment, the fertilizercomposition stabilizer material is: HTC and SGA. In one embodiment, thefertilizer composition stabilizer material is: HTC and ESP. In oneembodiment, the fertilizer composition stabilizer material is: HTC andinert agents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:apatite and bauxite. In one embodiment, the fertilizer compositionstabilizer material is: apatite and phosphate compounds. In oneembodiment, the fertilizer composition stabilizer material is: apatiteand salts of organic acids. In one embodiment, the fertilizercomposition stabilizer material is: apatite and red lime. In oneembodiment, the fertilizer composition stabilizer material is: apatiteand TCA. In one embodiment, the fertilizer composition stabilizermaterial is: apatite and aluminum hydroxide. In one embodiment, thefertilizer composition stabilizer material is: apatite and SGA. In oneembodiment, the fertilizer composition stabilizer material is: apatiteand ESP. In one embodiment, the fertilizer composition stabilizermaterial is: apatite and inert agents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:bauxite and phosphate compounds. In one embodiment, the fertilizercomposition stabilizer material is: bauxite and salts of organic acids.In one embodiment, the fertilizer composition stabilizer material is:bauxite and red lime. In one embodiment, the fertilizer compositionstabilizer material is: bauxite and TCA. In one embodiment, thefertilizer composition stabilizer material is: bauxite and aluminumhydroxide. In one embodiment, the fertilizer composition stabilizermaterial is: bauxite and SGA. In one embodiment, the fertilizercomposition stabilizer material is: bauxite and ESP. In one embodiment,the fertilizer composition stabilizer material is: bauxite and inertagents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:phosphate compounds and salts of organic acids. In one embodiment, thefertilizer composition stabilizer material is: phosphate compounds andred lime. In one embodiment, the fertilizer composition stabilizermaterial is: phosphate compounds and TCA. In one embodiment, thefertilizer composition stabilizer material is: phosphate compounds andaluminum hydroxide. In one embodiment, the fertilizer compositionstabilizer material is: phosphate compounds and SGA. In one embodiment,the fertilizer composition stabilizer material is: phosphate compoundsand ESP. In one embodiment, the fertilizer composition stabilizermaterial is: phosphate compounds and inert agents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:salts of organic acids and red lime. In one embodiment, the fertilizercomposition stabilizer material is: salts of organic acids and TCA. Inone embodiment, the fertilizer composition stabilizer material is: saltsof organic acids and aluminum hydroxide. In one embodiment, thefertilizer composition stabilizer material is: salts of organic acidsand SGA. In one embodiment, the fertilizer composition stabilizermaterial is: salts of organic acids and ESP. In one embodiment, thefertilizer composition stabilizer material is: salts of organic acidsand inert agents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:red lime and aluminum hydroxide. In one embodiment, the fertilizercomposition stabilizer material is: red lime and SGA. In one embodiment,the fertilizer composition stabilizer material is: red lime and ESP. Inone embodiment, the fertilizer composition stabilizer material is: redlime and inert agents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:aluminum hydroxide and SGA. In one embodiment, the fertilizercomposition stabilizer material is: aluminum hydroxide and ESP. In oneembodiment, the fertilizer composition stabilizer material is: aluminumhydroxide and inert agents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:SGA and, ESP. In one embodiment, the fertilizer composition stabilizermaterial is: SGA and inert agents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:three of: BR; LDH; HTC; apatite; bauxite; phosphate compounds; salts oforganic acids; red lime; TCA; aluminum hydroxide; SGA, ESP, and inertagents (e.g. sand, clay).

In some embodiments, the fertilizer composition stabilizer material is:BR; LDH; and HTC. In some embodiments, the fertilizer compositionstabilizer material is: BR; LDH; and apatite. In some embodiments, thefertilizer composition stabilizer material is: BR; LDH; and bauxite. Insome embodiments, the fertilizer composition stabilizer material is: BR;LDH; and phosphate compounds. In some embodiments, the fertilizercomposition stabilizer material is: BR; LDH; and salts of organic acids.In some embodiments, the fertilizer composition stabilizer material is:BR; LDH; and red lime. In some embodiments, the fertilizer compositionstabilizer material is: BR; LDH; and TCA. In some embodiments, thefertilizer composition stabilizer material is: BR; LDH; and aluminumhydroxide. In some embodiments, the fertilizer composition stabilizermaterial is: BR; LDH; and SGA. In some embodiments, the fertilizercomposition stabilizer material is: BR; LDH; and ESP. In someembodiments, the fertilizer composition stabilizer material is: BR; LDH;and inert agents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:LDH; apatite; and bauxite. In one embodiment, the fertilizer compositionstabilizer material is: LDH; apatite; and phosphate compounds. In oneembodiment, the fertilizer composition stabilizer material is: LDH;apatite; and salts of organic acids. In one embodiment, the fertilizercomposition stabilizer material is: LDH; apatite; and red lime. In oneembodiment, the fertilizer composition stabilizer material is: LDH;apatite; and TCA. In one embodiment, the fertilizer compositionstabilizer material is: LDH; apatite; and aluminum hydroxide. In oneembodiment, the fertilizer composition stabilizer material is: LDH;apatite; and SGA. In one embodiment, the fertilizer compositionstabilizer material is: LDH; apatite; and ESP. In one embodiment, thefertilizer composition stabilizer material is: LDH; apatite; and inertagents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:apatite; bauxite; and phosphate compounds. In one embodiment, thefertilizer composition stabilizer material is: apatite; bauxite; andsalts of organic acids. In one embodiment, the fertilizer compositionstabilizer material is: apatite; bauxite; and red lime. In oneembodiment, the fertilizer composition stabilizer material is: apatite;bauxite; and TCA. In one embodiment, the fertilizer compositionstabilizer material is: apatite; bauxite; and aluminum hydroxide. In oneembodiment, the fertilizer composition stabilizer material is: apatite;bauxite; and SGA. In one embodiment, the fertilizer compositionstabilizer material is: apatite; bauxite; and ESP. In one embodiment,the fertilizer composition stabilizer material is: apatite; bauxite; andinert agents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:bauxite; phosphate compounds; and salts of organic acids. In oneembodiment, the fertilizer composition stabilizer material is: bauxite;phosphate compounds; and red lime. In one embodiment, the fertilizercomposition stabilizer material is: bauxite; phosphate compounds; andTCA. In one embodiment, the fertilizer composition stabilizer materialis: bauxite; phosphate compounds; and aluminum hydroxide. In oneembodiment, the fertilizer composition stabilizer material is: bauxite;phosphate compounds; and SGA. In one embodiment, the fertilizercomposition stabilizer material is: bauxite; phosphate compounds; andESP. In one embodiment, the fertilizer composition stabilizer materialis: bauxite; phosphate compounds; and inert agents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:phosphate compounds; salts of organic acids; and red lime. In oneembodiment, the fertilizer composition stabilizer material is: phosphatecompounds; salts of organic acids; and TCA. In one embodiment, thefertilizer composition stabilizer material is: phosphate compounds;salts of organic acids; and aluminum hydroxide. In one embodiment, thefertilizer composition stabilizer material is: phosphate compounds;salts of organic acids; and SGA. In one embodiment, the fertilizercomposition stabilizer material is: phosphate compounds; salts oforganic acids; and ESP. In one embodiment, the fertilizer compositionstabilizer material is: phosphate compounds; salts of organic acids; andinert agents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:salts of organic acids; red lime; and TCA. In one embodiment, thefertilizer composition stabilizer material is: salts of organic acids;red lime; and aluminum hydroxide. In one embodiment, the fertilizercomposition stabilizer material is: salts of organic acids; red lime;and SGA. In one embodiment, the fertilizer composition stabilizermaterial is: salts of organic acids; red lime; and ESP. In oneembodiment, the fertilizer composition stabilizer material is: salts oforganic acids; red lime; and inert agents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:red lime; TCA; and aluminum hydroxide. In one embodiment, the fertilizercomposition stabilizer material is: red lime; TCA; and SGA. In oneembodiment, the fertilizer composition stabilizer material is: red lime;TCA; and ESP. In one embodiment, the fertilizer composition stabilizermaterial is: red lime; TCA; and inert agents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:TCA; aluminum hydroxide; and SGA. In one embodiment, the fertilizercomposition stabilizer material is: TCA; aluminum hydroxide; and ESP. Inone embodiment, the fertilizer composition stabilizer material is: TCA;aluminum hydroxide; and inert agents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:aluminum hydroxide; SGA, and ESP. In one embodiment, the fertilizercomposition stabilizer material is: aluminum hydroxide; SGA, and inertagents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:SGA, ESP, and inert agents (e.g. sand, clay). In one embodiment, thefertilizer composition stabilizer material is: BR; apatite; and TCA. Inone embodiment, the fertilizer composition stabilizer material is:apatite; bauxite; and TCA. In one embodiment, the fertilizer compositionstabilizer material is: BR; bauxite, and TCA.

In one embodiment, the fertilizer composition stabilizer material isfour of: BR; LDH; HTC; apatite; bauxite; phosphate compounds; salts oforganic acids; red lime; TCA; aluminum hydroxide; SGA, ESP, and inertagents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material isfive of: BR; LDH; HTC; apatite; bauxite; phosphate compounds; salts oforganic acids; red lime; TCA; aluminum hydroxide; SGA, ESP, and inertagents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is sixof: BR; LDH; HTC; apatite; bauxite; phosphate compounds; salts oforganic acids; red lime; TCA; aluminum hydroxide; SGA, ESP, and inertagents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material isseven of: BR; LDH; HTC; apatite; bauxite; phosphate compounds; salts oforganic acids; red lime; TCA; aluminum hydroxide; SGA, ESP, and inertagents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material iseight of: BR; LDH; HTC; apatite; bauxite; phosphate compounds; salts oforganic acids; red lime; TCA; aluminum hydroxide; SGA, ESP, and inertagents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material isnine of: BR; LDH; HTC; apatite; bauxite; phosphate compounds; salts oforganic acids; red lime; TCA; aluminum hydroxide; SGA, ESP, and inertagents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is tenof: BR; LDH; HTC; apatite; bauxite; phosphate compounds; salts oforganic acids; red lime; TCA; aluminum hydroxide; SGA, ESP, and inertagents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material iseleven of: BR; LDH; HTC; apatite; bauxite; phosphate compounds; salts oforganic acids; red lime; TCA; aluminum hydroxide; SGA, ESP, and inertagents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material istwelve of: BR; LDH; HTC; apatite; bauxite; phosphate compounds; salts oforganic acids; red lime; TCA; aluminum hydroxide; SGA, ESP, and inertagents (e.g. sand, clay).

In one embodiment, the fertilizer composition stabilizer material is:BR; LDH; HTC; apatite; bauxite; phosphate compounds; salts of organicacids; red lime; TCA; aluminum hydroxide; SGA, ESP, and inert agents(e.g. sand, clay).

Without being bound by a particular mechanism or theory, it is believedthat in one potential pathway, certain stabilizer materials may act assuppressants, causing a chemical inhibition of ammonium nitrate, thuspreventing it from being utilized as an oxidizing material in anexplosive device.

Without being bound by a particular mechanism or theory, it is believedthat in another potential pathway, certain stabilizer materials may actas diluents, causing a mechanical inhibition of ammonium nitrate, thuspreventing it from being utilized as an oxidizing material in anexplosive device.

Without being bound by a particular mechanism or theory, it is believedthat in yet another pathway, certain stabilizer materials may act ascarbonating agents, such that carbon dioxide produced by the stabilizermaterial replaces/excludes oxygen needed for an explosion tocontinue/propagate, thus resulting in no increase in energy (needed topropagate the explosion).

Without being bound by a particular mechanism or theory, it is believedthat in yet another pathway, certain stabilizer materials may act ashydrates, such that during an explosion event (increase in energy) thestabilizer material produces water vapor, which also acts to excludeoxygen or quench heat coming from the reaction so that resultingexothermic energy is reduced (and the material does not explode),thermal moderators.

Without being bound by a particular mechanism or theory, it is believedthat in yet another pathway, certain stabilizer materials may act inaccordance with an acid/base mechanism, such that the stabilizermaterial is basic or releases a base when at reaction conditions thuspreventing ammonium nitrate from proceeding to nitric acid (thus thereaction will not proceed or take place). In some embodiments, thestabilizer material(s) act as a thermal moderator to adsorb energy, thusreducing the explosive force. In some embodiments, the stabilizermaterials act as oxygen displacers by pushing out oxygen and replace thegas with a non-combustible (e.g. CO₂).

Without being bound by a particular mechanism or theory, the addition ofbauxite, bauxite residue, the products and/or by-products of to ammoniumnitrate fertilizer can provide a retardant for its potential misuse asan ingredient in homemade explosives.

Without being bound by a particular mechanism or theory, in someembodiments a stabilizer material is added to the fertilizer, where thechemical species in the stabilizer material acts to absorb some of theenergy released if the fertilizer is used in ammonium nitrate fuel oil(ANFO) improvised explosive devices or other ammonium nitrate fuelcombinations used for explosives. Specifically, in this potentialmechanistic pathway, the chemical stabilizer materials are believed toabsorb a portion of the heat released during ammonium nitrate-fueldetonations such that the stabilizer materials reduce the finalequilibrium temperature of the system via both sensible heat absorptionand endothermic chemical reactions. Along with the energy absorptionproperty, the presence of stabilizer material solid particles isbelieved to reduce the energy density of the mixture via dilution of thefiller material.

In some embodiments, the fertilizer composition includes a pH adjustingcomponents. Non-limiting examples of pH adjusting components include:nitric acid, phosphoric acid, bauxite residue.

In some embodiments, the fertilizer composition includes a plantnutrient. Non-limiting examples of plant nutrients include: N, P, K, Mg,Ca, K, trace elements (Fe, Mn, metals present in the stabilizer materialcompounds), and combinations thereof.

These and other aspects, advantages, and novel features of thetechnology are set forth in part in the description that follows andwill become apparent to those skilled in the art upon examination of thefollowing descriptions and Figures, or is learned by practicing theembodiments of the instant disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a schematic of an embodiment of a blast test article inaccordance with the instant disclosure.

FIG. 2 depicts a schematic cut-away side view of the blast test articleof FIG. 1, depicting the booster and fertilizer composition to betested.

FIG. 3 is a chart depicting the relative specific impulse of prilledfertilizer compositions, with the specific impulse from eachoverpressure sensor. For prilled samples, referring to FIG. 3, blasttests were completed and specific impulse values were calculated formultiple test articles including: two test articles with commerciallyavailable AN fertilizer from vendor 1 (Control 1); three test articleswith commercially available AN fertilizer from vendor 2 (Control 2); onetest article with a commercially available “blast resistant” ANfertilizer; two test articles of AN fertilizer from vendor 1 coated withbauxite residue (having 15 wt. % phosphate from a neutralization stepwith phosphoric acid), and one test article of AN fertilizer from vendor2 coated with bauxite residue (having 15 wt. % phosphate). As depictedin FIG. 3, BR coated prills performed better than any of thecommercially available AN prills, with two test articles of BR coatedprills out-performing the commercially available “blast resistant”fertilizer.

FIG. 4 is a chart depicting the relative Specific Impulse of groundfertilizer compositions, with the specific impulse from eachoverpressure sensor (two sensors for each blast test). Fertilizercompositions were prepared in accordance with the Examples. Blast testswere conducted in accordance with Examples. Referring to FIG. 4, blasttests were completed and specific impulse values were calculated formultiple test articles including: two test articles with commerciallyavailable AN fertilizer from vendor 1 (Control 1); three test articleswith commercially available AN fertilizer from vendor 2 (Control 2); onetest article with a commercially available “blast resistant” ANfertilizer (in ground form); two test articles of AN fertilizer fromvendor 1 blended with bauxite residue (having 15 wt. % nitrate, presentvia addition of aluminum hydroxide and anthropogenic exposure toatmospheric carbon dioxide), and two test articles of AN fertilizer fromvendor 2 blended with 25 weight percent of bauxite residue (having 15wt. % phosphate).

As depicted in FIG. 4, the fertilizer compositions of BR and ammoniumnitrate outperformed the commercially available AN. The commerciallyavailable “blast resistant” BR coated prills performed slightly betterthan ammonium nitrate from vendor 1 blended with bauxite residue havingnitrate therein. Mean specific impulse values are provided in the tablein the corresponding Examples section. Based on the results from thisset of experiments, further blast testing was completed using onlyground materials in the test articles, since any reduction in specificimpulse realized in the ground form would translate to the prilled orpelletized form.

FIG. 5 is a chart depicting booster size (in grams) as a function ofcharge diameter (in inches) for a fertilizer composition of 25 wt. %hydrotalcites where solid circles indicate detonation while an “x”indicates no detonation. The plotted line depicts detonation versus nondetonation region at a sensitivity of +50 g increase in booster size.

FIG. 6 is a chart depicting booster size (in grams) as a function ofcharge diameter (in inches) for a fertilizer composition of 22.5 wt. %hydrotalcites where solid circles indicate detonation while an “x”indicates no detonation. The plotted line depicts detonation versus nondetonation region at a sensitivity of +50 g increase in booster size.

FIG. 7 is a graph is a chart depicting booster size (in grams) as afunction of charge diameter (in inches) for a fertilizer composition of20 wt. % hydrotalcites where solid circles indicate detonation while an“x” indicates no detonation. The plotted line depicts detonation versusnon detonation region at a sensitivity of +50 g increase in boostersize.

FIG. 8 is a graph is a chart depicting booster size (in grams) as afunction of charge diameter (in inches) for a fertilizer composition of20; 22.5 and 25 wt. % HTC-PO4. The plotted line depicts detonationversus non detonation region at a sensitivity of +50 g increase inbooster size.

FIG. 9 is a graph depicting the specific impulse for test articles thatresulted in a non-perforation of the witness plate, where “x” refers to25 wt. % HTC, diamond depicts 22.5 wt. % and dashes depict 20 wt. %.

FIG. 10 is a graph depicting specific impulse at different boostersizes, where “x” refers to the standard fuel oil content (i.e. 6%, ascompared to AN content); diamond refers to 50% more stoichiometric fueloil (i.e. 9% as compared to the AN content); and where dash refers to100% fuel oil (i.e. 12 wt. % as compared to AN content).

FIG. 11 is a graph depicting the specific impulse at different boostersizes for 20 wt. % HTC in a 5″ diameter tube (test article).

FIG. 12 is a graph that illustrates the specific impulse of HTC at 22.5%(square) and 25% (diamonds) concentration at an 8″ diameter with boostersize ranging from 300-600 g.

FIG. 13 is a graph that depicts the global cliff of all the stabilizermaterials. The graph is plotted as number of sample against specificimpulse. This data represents all data analyzed in the Blast Suppressionand Desensitization Example and shows the distinction between nonperforation and perforation. The data consists of HTC-PO₄, Apatite andHTC PO₄-15%/BR 10% mixture.

FIG. 14 is a graph that depicts the trends of specific impulse reductionin relation to concentration in percent. Listed in the graph areHTC-PO₄—22.5% (diamond), HTC-PO₄—20% (X), HTC-PO₄—15% (square),HTC-PO₄—10% (triangle) and AN (circle)

FIG. 15 is a graph that illustrates the percent reduction of specificimpulse when compared to concentration of 10, 15, 17.5, 20, 22.5 and25%.

FIG. 16 is a graph depicts the specific impulse of stabilizer materialsthat showed non perforation at different booster levels at differentconcentration. X=HTC-PO₄—25%; Triangle=Apatite; Dash—HTC-PO₄—15%/BR 10%,

FIG. 17 is a graph that depicts perforating versus non-perforating ofstabilizer materials at different booster charge and percent stabilizermaterial at 5″ diameter with a 100% accuracy. Solids symbols indicateperforation; open symbols depicts non perforation. Circle=HTC PO₄—25%;Diamond=Apatite—25%; Square=HTC PO₄—15%/BR 10%

FIG. 18 is a graph that depicts perforating versus non-perforating ofstabilizer materials at different booster charge and percent stabilizermaterial at 6″ diameter. Solids symbols indicate perforation; opensymbols depicts non perforation.

FIG. 19 is a graph that depicts perforating versus non-perforating ofstabilizer materials at different booster charge and percent stabilizermaterial at 8″ diameter. Solids symbols indicate perforation; opensymbols depicts non perforation.

FIG. 20 is a graph that depicts specific impulse at different boostercharge for HTC PO₄ at different concentration; X=25%; dash=20%;diamond=22.5%. The graph also illustrates the specific impulse ofalternate product (ALT PRDT) at 13.25 kPa·ms/kg and control-AN at 15.5kPa·ms/kg.

DETAILED DESCRIPTION Example: Thermodynamic Calculations

A series of isenthalpic equilibrium calculations were performed onmixtures of different materials in combination with ammonium nitrate. Inthis method, a mixture is put into a “box” that retains all of theenergy of the system. The equilibrium chemical composition of themixture was calculated via a computer model and the energy releasedcauses the system temperature to rise.

In completing the computer model and performing the calculation in thisway, pure ammonium nitrate decomposes into N₂, H₂, and H₂O (all lowerenergy than AN) and the energy that is released increase the gastemperature (i.e. in the box) to 970° C. Addition of other components tothe system can now be explored to see their effect on the final systemtemperature. For example, a 1:1 mixture of AN and SiO2 will result inthe final composition of N₂, H₂, H₂O and SiO₂ at 604° C. The lowertemperature is due to the presence of the SiO₂ as an inert material thatabsorbs some of the energy released from AN decomposition. The energyabsorption can be enhanced if the stabilizer material itself is notinert, but can react to change state (and/or degrade to form othercompounds). For example, a 1:1 mixture of AN with chalk (CaCO3) gives afinal composition N₂, H₂, H₂O, CaO, and CO₂ at a temperature of 585° C.Some of the AN decomposition energy is used to convert chalk to lime(CaO) and CO₂ via the endothermic reaction CaCO₃→CaO+CO₂.

In some embodiments, bauxite residue (BR) is a mixture of inertmaterials (SiO₂, TiO₂, Fe₂O₃, etc.) and components which may act as“energy absorbers” (Al(OH)₃, AlOOH, Fe₂O₃, H₂O, etc.) the final systemtemperature for a 1:1 mixture of AN+BR is 711° C. In addition to BR, anumber of other materials were evaluated as energy absorbers. The bestperformer (i.e. at a 1:1 mix) is Bayer process hydrate (Al(OH)₃) with afinal system temperature of 233° C. Some other attractive materialscould be hydrated lime (Ca(OH)₂) and gypsum (CaSO₄*2H₂O). The results ofthe energy absorption performance calculations are summarized in thefollowing table below, where the lower the final temperature, the“better” the performance.

Final Temp Material* (° C.) % Reduction AN Control (NH₄NO₃) 970 N/A -Control Bauxite Residue 711 27% (mixed metal oxides, as above) BayerProcess Hydrate 233 76% (Al(OH)₃) Silicon Dioxide 601 38% (SiO₂) CalciumCarbonate 585 40% (CaCO₃) Calcium Sulfate Hydrate 369 62% (CaSO₄*2H₂O)Calcium Hydroxide 497 51% (Ca(OH)₂) *Control was 100% AN, all other“Materials” modeled were in a 1:1 concentration with AN

All additions to AN performed better (resulted in lower equilibriumtemperatures) as compared to the pure AN and some additions to ANperformed better than others. Percent reductions in equilibriumtemperature were computed for the isenthalpic models, and the percentreduction values ranged from a 27% reduction (bauxite residue) to a 76%reduction (aluminum hydroxide). The general trends observed from thecomputer modeling of isenthalpic equilibrium of various AN data wereused to down-select constituents as stabilizer materials to ANfertilizer. Without being bound by a particular mechanism or theory, itis believed that if a constituent of a material lowered the isenthalpicequilibrium temperature, then the resulting material would alsopotentially prevent the combustion of ammonium nitrate (and thus,potentially provides a blast suppression and/or desensitizationmechanism to ammonium nitrate fertilizer(s)). For example, constituentshaving metal oxides, hydrates, carbonates, and hydroxides were exploredas fertilizer compositions (i.e. experiments performed include blasttests to explore potential of blast suppression and/or desensitizationof stabilizer materials in AN fertilizer).

Example: Standard Operating Procedure for Blast Tests

Test articles refer to the container (PVC pipe), a mild steel plate(called a witness plate), fertilizer composition (stabilizer materialand AN mixed with 6 wt. % fuel oil of AN), and a booster (includes C4explosive in a plastic storage cup). A schematic of a test article isdepicted in FIG. 1, while the innards of each test article, includingthe detonator, booster, and fertilizer composition are shown in FIG. 2.

Sample Preparation:

To make a fertilizer composition for the test article, ammonium nitratefertilizer prills were dry ground using a ball mill to make a less than20 mesh (<800 micrometers). Then, the AN powder was dry blended with thestabilizer material powder.

Samples containing iHTC with phosphate had a 15 wt. % phosphate. Bauxiteresidue samples had either phosphate (i.e. 5-10% wt. %) or nitrate (i.e.5-10 wt. %) Sample mixtures were dry weighed, and fuel oil was added (6wt. %) in accordance with the AN content. For all tests, the contents ofeach article included a ratio of 6% fuel oil to 94% ammonium nitrate(based on mass). The resulting fertilizer/fuel oil composition wasmixed/blended for at least 30 minutes and checked for caking with visualobservation.

Each test article was weighed empty using a scale with an accuracy of+/−0.2 grams. The resulting mixture was added to each container (PVCwith glued end cap) to within 25 mm of top edge. Each filled testarticle (ammonium nitrate and stabilizer material, mixed with fuel oil)was weighed on a scale having an accuracy of +/−0.1 ounce.

Each test article was left to stand for at least 12 hours prior totesting with a covering (e.g. plastic bag) applied to prevent ambientmoisture from entering the test article. Just prior to testing, thebooster (C4 in a plastic cup) was inserted flush with the top of thepipe, with the detonator wire attached to the booster.

Boosters for each test article were prepared in small plastic storagecups. A predetermined amount of C4 was measured into each cup. A C4booster was added to a 5″ diameter tube with blast material to betested. The total weight of the tube was approximately eight kg(including the blast material).

Each test article included a 0.25 inch thick mild steel plate (called awitness plate), with a PVC Pipe, base/end cap. However, the base capswere domed and would not sit vertically on the witness plate. Anadditional section of 6″ PVC pipe, ˜3″ in length was cut (split) andslipped over the outer surface of the test article. This piece providedgood stability to the test article for filling and testing. The testarticle was placed onto a 4½″ stack thick piece of foam (12 inches×12inches) on a level sand pit.

Filled test articles were placed onto witness plates and positioned andcentered on the witness plate. Cable (Cat6 cable) was routed from theshelter to Over Pressure probes.

The detonator was placed into the booster, the charge was armed, and thebooster was detonated. For each test article, the detonator wasExploding Bridge Wire (EBW) Type RP-83.

Blast suppression was measured via two blast pressure probes (PCBmodel), positioned at a distance of 7 m from the test article. Coaxialcable ran from each probe (2-channel, 12 bit, IEPE, 100 kHz) to acomputer. Steel rods were positioned between the probes and the target(i.e. test article) to deflect any possible shrapnel.

For each test, two blast pressure probes were used to measure thepressure versus time of each explosion (kPa*ms). The resulting pressurereadings were used to compute the specific impulse of the fertilizercomposition for each test article. Blast overpressure (i.e. impulsepressure) was collected for each test article.

This data was then integrated by standard means and then divided by theamount of ammonium nitrate present to generate a “specific impulse”(i.e. maximum pressure reading for each blast test impulse). These werethen measured against a reference specific impulse of ANFO itself orammonium nitrate combined with other fuels.

Without being bound by a particular mechanism or theory, stabilizermaterials with a specific impulse at approximately the same level as thebaseline (AN controls) are considered “inert”, in that it is believedthat these materials affect the impulse at the same levels as theconcentration dictates (i.e. operate by a mechanical “filler”mechanism).

Without being bound by a particular mechanism or theory, measurementsbelow the baseline results are considered “suppressants”, in that it isbelieved that these materials affect the impulse by a chemical reactionor mechanism independent, or in combination with, a dilution factor.

Example: Blast Test—Ground Vs. Coated Prilled Ammonium Nitrate

It is noted that test articles which had materials that were powdered(ground to a fine texture) produced higher specific impulse values thanmaterials that were produced with prills.

Average Specific Prill Specific Specific Impulse Test Articles Impulse AImpulse B (kPa · ms/kg) AN V2, BR2 0.81 0.92 0.86 AN V1, BR2 0.95 1.000.98 ALT PRDT 1.23 1.34 1.29 AN V1, BR2 1.34 1.37 1.36 CRTL-V1 2.26 2.322.29 CRTL-V1 2.70 2.66 2.68 CRTL-V2 2.85 2.89 2.87 CRTL-V2 3.01 3.023.01 CRTL-V2 3.21 3.29 3.25 Average Specific Ground Specific SpecificImpulse Test Articles Impulse A Impulse B (kPa · ms/kg) AN V1, BR1 12.6712.60 12.64 ALT PRDT 12.02 12.47 12.25 AN V1, BR1 13.31 13.32 13.31 ANV2, BR2 14.50 14.49 14.49 AN V2, BR2 14.63 14.79 14.71 CTRL-V2 14.9715.51 15.24 CTRL-V1 15.29 15.27 15.28 CTRL-V1 N/A* 15.49 15.49 CTRL-V215.52 15.65 15.58 CTRL-V2 15.80 15.67 15.74 N/A* = probe wasdisconnected - no reading was obtained

Example: Blast Test—Different Stabilizer Materials

In order to identify stabilizer materials with blast suppression and/ordesensitization characteristics, various stabilizer materials weretested (each at 25 wt. %), in a 5″ diameter tube with 200 g booster. Thespecific impulse was calculated for each test article and is presentedin the table below, which also provides the mean impulse (obtained as anaverage of the overpressure sensor measurements from each detonation)and the visual observation of the state of the witness plate(perforated, non-perforated).

Mean Stabilizer Sp. Imp. Impulse Witness Impulse 1 Impulse 2 # materials(kPa*ms/kg) (kPa*ms) Plate (kPa*ms) (kPa*ms) 1 AN 14.7 110.9 perf 108.7113.1 2 AN 14.7 111.5 perf 109.6 113.3 3 AN 14.2 108.8 perf 107.5 110.14 AN 14.3 110.9 perf 108.8 113.1 5 Bauxite 12.1 84.2 perf 83.1 85.3 6Bauxite 13.2 86.5 perf 85.3 87.8 7 Bauxite 13.3 87.0 perf 85.1 88.8 8Bauxite 12.2 83.5 perf 81.6 85.5 9 BR1 (NO3) 15.1 90.4 perf 87.9 92.8 10BR1 (NO3) 14.4 86.7 perf 85.9 87.4 11 BR1(NO3) n/a n/a no perf n/a n/a12 BR1(NO3) 15.3 90.5 perf 88.9 92.0 13 BR2 (PO4) 12.7 86.1 perf 85.287.1 14 BR2(PO4) 11.9 83.7 perf 82.0 85.4 15 BR2(PO4) n/a n/a no perfn/a n/a 16 BR2(PO4) 12.4 85.1 perf 83.3 86.9 17 HTC-CO3 0.0 19.3 no perf18.9 19.7 18 HTC-CO3 −0.2 18.3 no perf 18.2 18.4 19 HTC-CO3 0.0 19.3 noperf 18.7 19.8 20 HTC-PO4 0.9 23.2 no perf 22.9 23.5 21 HTC-PO4 0.6 22.2no perf 21.9 22.6 22 HTC-PO4 1.2 24.6 no perf 24.2 25.1 23 HTC-PO4 1.023.9 no perf 23.9 n/a 24 Hydrate 13.5 83.7 perf 82.7 84.8 25 Hydrate13.4 83.2 perf 81.8 84.7 26 Hydrate 13.3 81.8 perf 79.7 83.9 27 Hydrate13.2 80.2 perf 78.4 81.9 28 Oxalate 13.5 81.6 perf 80.3 83.0 29 Oxalate12.9 80.8 perf 79.4 82.2 30 Oxalate 13.4 81.3 perf 79.9 82.7 31 Oxalate13.4 83.1 perf 80.3 85.9 32 Sand 14.5 91.6 perf 90.0 93.2 33 Sand 14.491.2 perf 89.7 92.7 34 Sand 13.8 90.7 perf 88.9 92.4 35 Sand 13.3 87.6perf 85.9 89.4 36 SGA 10.8 74.0 perf 73.3 74.7 37 SGA 9.7 71.9 perf 70.873.0 38 SGA 9.8 71.2 perf 69.2 73.1 39 SGA 10.7 73.3 perf 72.1 74.6

It is noted that for runs 11 and 15, the booster (C4) did not detonate,which resulted in no perforation of the witness plate.

In order to account for the booster shot in the specific impulsecalculation, multiple booster shots (6) were completed at variousamounts of booster. The results were linear—as the amount of boosterincreased, so too did the resulting specific impulse.

Example: Blast Test—Blast Suppression and Desensitization

In order to identify blast suppression and desensitization parameters,three variables were tested under this set of experiments, including:

(1) fertilizer composition (i.e. AN+(a) stabilizer material 1 (HTC atdifferent wt. %), (2) stabilizer material 2 (apatite), and (3)stabilizer material 3 (combined 15 HTC/10BR);(2) booster size/quantity (e.g. 200 g, 300 g, 400 g, 600 g, 800 g); and(3) tube diameter of the test article (i.e. 5 inch, 6 inch, or 8 inchdiameter).

Diluent Booster Tube Witness Sp. Imp. # Sample (%) (g) (in) Plate (kPa ·ms/kg) 1 HTC 10 200 5 Perf 13.68 2 HTC 15 400 5 Perf 12.66 3 HTC 15 2005 Perf 10.61 4 HTC 15 200 5 Perf 13.61 5 HTC 17.5 200 5 Perf 12.92 6 HTC20 200 6 Perf 11.48 7 HTC 20 200 6 Perf 12.44 8 HTC 20 500 5 Perf 12.409 HTC 20 400 5 Perf 12.08 10 HTC 20 400 5 Perf 9.29 11 HTC 22.5 400 6Perf 11.41 12 HTC 22.5 400 8 Perf 9.64 13 HTC 22.5 350 8 Perf 10.30 14HTC 25 600 8 Perf 9.43 15 HTC 25 500 8 Perf 8.11 16 HTC 20 200 5 No perf3.53 17 HTC 20 300 5 No perf 3.57 18 HTC 22.5 400 5 No perf 3.99 19 HTC22.5 600 5 No perf 4.52 20 HTC 22.5 700 5 No perf 4.86 21 HTC 22.5 300 6No perf 2.66 22 HTC 22.5 300 8 No perf 4.02 23 HTC 25 200 5 No perf 1.5624 HTC 25 300 5 No perf 1.76 25 HTC 25 400 5 No perf 2.10 26 HTC 25 5005 No perf 2.60 27 HTC 25 600 5 No perf 4.59 28 HTC 25 700 5 No perf 5.1529 HTC 25 400 6 No perf 2.79 30 HTC 25 600 6 No perf 2.50 31 HTC 25 4008 No perf 4.12 32 HTC 25 450 8 No perf 4.25 33 HTC 25 400 5 No perf 2.8634 HTC 25 600 5 No perf 3.48 35 HTC 25 400 5 No perf 2.01 36 HTC 25 6005 No perf 2.49 37 HTC 25 800 5 No perf 4.17 38 Apatite 25 200 5 No perf1.74 39 Apatite 25 400 5 No perf 2.19 40 15HTC/10BR 25 200 5 No perf1.41 41 15HTC/10BR 25 400 5 No perf 2.32

In order to account for the booster shot in the specific impulsecalculation, multiple booster shots (16) were completed at variousamounts of booster. The results were linear—as the amount of boosterincreased, so too did the resulting specific impulse.

It is noted that the BR in runs 40 and 41 had a phosphate content of5-15 wt. %.

It is noted that runs 33-36 had increased fuel oil in the fertilizercomposition. Run 33 and 34 were 50% fuel oil (i.e. 9 wt % fuel oilcompared to AN content) and runs 35 and 36 were 100% fuel oil (i.e. 12wt. % fuel oil, as compared to AN content).

Data Comparison:

The below table illustrates all stabilizer materials in ground form atthe standard operating procedure of 5″ diameter and 200 g booster size;with the exception of HTC-PO4-22.5%. This sample was a 5″ tube withbooster sizes of 300, 400, 600, and 700.

Stabilizer Avg. St. material Sp. Imp. Sp. Imp. Dev. BR1-(PO₄) 12.6412.98 0.48 13.31 Bauxite-25% 12.1 12.7 0.6 12.2 13.2 13.3 Oxalate-25%12.9 13.3 0.3 13.4 13.4 13.5 Apatite-25% 1.7 1.7 HTC-PO₄-15%/BR-10% 1.41.4 BR2 14.49 14.60 0.15 14.71 BR1-(NO₃) 14.4 14.9 0.4 15.1 15.3 BR2-PO₄11.9 12.3 0.4 12.4 12.7 SGA-25% 9.7 10.2 0.6 9.8 10.7 10.8 Hydrate-25%13.2 13.3 0.1 13.3 13.4 13.5 Sand-23% 13.3 14.0 0.5 13.8 14.4 14.5HTC-CO₃-25% −0.2 0.0 0.1 0.0 0.0 HTC-PO₄-22.5% 2.7 6.4 3.4 4.0 4.0 4.54.9 9.6 10.3 11.4 HTC-PO₄-17.5% 12.9 12.9 HTC-PO₄-25% 0.6 1.2 0.4 0.91.0 1.2 1.6 1.8 HTC-PO₄-10% 13.7 13.7 HTC-PO₄-15% 10.6 12.3 1.5 12.713.6 HTC-PO₄-20% 3.5 9.3 4.4 3.6 11.5 12.1 12.4 12.4 AN 14.2 15.02 0.5714.3 14.7 14.7 15.24 15.28 15.49 15.58 15.74 CAN-27-G 13.25 13.25

For the following three sets of blast data, we note the hydrotalcite,hydrocalumite, red lime, and hydroxyapatite materials were obtained froman alumina refining process, unless otherwise indicated (i.e.“synthetic” refers to materials obtained via a commercial vendor).

As these materials were obtained via an alumina refining process,analytical data was compiled in order to better understand thecharacteristics of the aluminum byproduct material (e.g. as compared tocommercially available alternatives with high purity and low to nounavoidable minor components). Below, the analytical data is set forthfor the materials obtained via the alumina refining process, with minorvariations depicted for different batches of the same material.

Two batches of hydrotalcite were utilized in the following three blasttests. For the first batch of hydrotalcite: the density was measured at2.1135 g/cc, while the surface area was 30.8 m2/g. The average particlesize was measured at 12.98 microns. The x-ray diffraction noted thefollowing components: Major: Mg4Al2(OH)14.3H2O, Magnesium AluminumHydroxide Hydrate, Meixnerite and/or Mg4Al2(OH)12CO3.3H2O, MagnesiumAluminum Hydroxy Carbonate Hydrate and/or Mg6Al2CO3(OH)16.4H2O,Hydrotalcite, Trace possible: Ca3Al2(OH)12.

For the second batch of hydrotalcite: the density was measured at 2.0941g/cc, while the surface area was 29 m2/g. The average particle size wasmeasured at 12.31 microns. The x-ray diffraction noted the followingcomponents: Major: Mg6Al2(CO3)(OH)16.4(H2O), Hydrotalcite and/orMg6Al2(OH)18.4.5H2O, Magnesium Aluminum Hydroxide Hydrate, Tracepossible: Ca3AlFe(SiO₄)(OH)8, Calcium Aluminum Iron Silicate Hydroxide.

For the bauxite residue material, the density was measured at 3.3441g/cc, while the surface area was 42.3 m2/g. The average particle sizewas measured at 4.892 microns. The x-ray diffraction noted the followingcomponents: Major: Fe2O3, Hematite; CaCO3, Calcium Carbonate; Minor:TiO2, Titanium Oxide, Rutile; FeO(OH), Goethite; Al(OH)3, Bayerite;AlO(OH), Boehmite; Trace possible: Al(OH)3, Gibbsite;Na8Si6Al6O24(OH)2(H2O)2, Sodium Silicon Aluminate.

For the apatite, two batches were utilized. For the first batch ofapatite material, the density was measured at 2.6645 g/cc, while thesurface area was 76 m2/g. The average particle size was measured at5.518 microns. The x-ray diffraction noted the following components:Major: Ca10(PO4)3(CO3)3(OH)2, Calcium Carbonate Phosphate Hydroxide;Mg6Al2(CO3)(OH)16.4(H2O), Hydrotalcite and/or Mg6Al2(OH)18.4.5H2O,Magnesium Aluminum Hydroxide Hydrate, with Minor possible: CaCO3,Calcium Carbonate.

For the second batch of apatite material, the density was measured at2.6443 g/cc, while the surface area was 89 m2/g. The average particlesize was measured at 5.367 microns. The x-ray diffraction noted thefollowing components: Major: Ca10(PO4)3(CO3)3(OH)2, Calcium CarbonatePhosphate Hydroxide; Mg6Al2(CO3)(OH)16.4(H2O), Hydrotalcite and/orMg6Al2(OH)18.4.5H2O, Magnesium Aluminum Hydroxide Hydrate, Minorpossible: CaCO3, Calcium Carbonate.

For the red lime, two batches were utilized.

For the first batch of red lime material, the density was measured at2.5621 g/cc, while the surface area was 4.1 m2/g. The average particlesize was measured at 20.62 microns. The x-ray diffraction noted thefollowing components: Major: CaCO3, Calcium Carbonate. Minor:Ca3AlFe(SiO4)(OH)8, Calcium Aluminum Iron Silicate Hydroxide. VerySmall: Ca(OH)2, Calcium Hydroxide. Trace: Mg6Al2(CO3)(OH)16.4(H2O),Hydrotalcite and/or Mg6Al2(OH)18.4.5H2O, Magnesium Aluminum Hydroxide.

For the second batch of red lime material, the density was measured at2.5658 g/cc, while the surface area was 4.7 m2/g. The average particlesize was measured at 12.43 microns. The x-ray diffraction noted thefollowing components: Major: CaCO3, Calcium Carbonate. Minor:Ca3AlFe(SiO4)(OH)8, Calcium Aluminum Iron Silicate Hydroxide. VerySmall: Ca(OH)2, Calcium Hydroxide. Trace: Mg6Al2(CO3)(OH)16.4(H2O),Hydrotalcite and/or Mg6Al2(OH)18.4.5H2O, Magnesium Aluminum Hydroxide.

Two batches of hydrocalumite were utilized.

For the first batch of hydrocalumite material, the density was measuredat 2.2296 g/cc, while the surface area was 10.4 m2/g. The averageparticle size was measured at 12.21 microns. The x-ray diffraction notedthe following components: Major: Ca(OH)2, Calcium Hydroxide; CaCO3,Calcium Carbonate; Ca4Al2(OH)12(CO3)(H2O)5, Calcium Aluminum HydroxideCarbonate Hydrate; Ca4Al2O6C12(H2O)10, Hydrocalumite, Minor possible:Mg6Al2(CO3)(OH)16.4(H2O), Hydrotalcite and/or Mg.

For the second batch of hydrocalumite material, the density was measuredat 2.2561 g/cc, while the surface area was 11.71 m2/g. The averageparticle size was measured at 16.31 microns. The x-ray diffraction notedthe following components: Major: Ca(OH)2, Calcium Hydroxide; CaCO3,Calcium Carbonate; Ca4Al2(OH)12(CO3)(H2O)5, Calcium Aluminum HydroxideCarbonate Hydrate; Ca4Al2O6C12(H2O)10, Hydrocalumite, Minor possible:Mg6Al2(CO3)(OH)16.4(H2O), Hydrotalcite and/or Mg.

Example: Blast Test—Blast Suppression and Desensitization

The below table illustrates experimental results from blast testscompleted on a control (AN) as compared to two stabilizer materials:hydrotalcite and hydroxyapatite in various forms (e.g. recovered from analumina production process, synthetic, etc) and at different weightpercent.

For this blast test, the fuel was fuel oil for all materials, though thebooster size varied (as indicated) and a few of the runs included largerdiameter tubes (e.g. 8 inches) as compared to the standard size (5″)utilized for many of the runs. The blast test components were preparedas previously indicated, according to the standard operating procedure.The specific impulse readings are provided below, along with acomparative view of the Reduction in Blast, measured as a percentageaccording to various SI baselines (e.g. 13.5, 10.0, and 8.0). When ablast test did not result in a reduction in specific impulse, thereduction percentage is indicated as “N/A”.

Reduction Reduction Reduction vs. 13.5 vs. 10.0 vs. 8.0 Booster Dia. Sp.Imp. Baseline Baseline Baseline Material (g) (in.) (kPa · ms/kg) (%) (%)(%) Ammonium Nitrate (control) 10 5 15.38 N/A N/A N/A Ammonium Nitrate(control) 10 5 15.37 N/A N/A N/A Ammonium Nitrate (control) 25 5 15.24N/A N/A N/A Ammonium Nitrate (control) 100 5 15.25 N/A N/A N/AHydrotalcite 17.5 wt % 200 5 1.01 92.5 89.9 87.3 Hydrotalcite 17.5 wt %300 5 7.92 41.3 20.8 1 Hydrotalcite 17.5 wt % 400 5 10.91 19.2 N/A N/AHydrotalcite 17.5 wt % 400 5 3.16 76.6 68.4 60.5 Hydrotalcite 25 wt. %400 5 1.76 87 82.4 78 Hydrotalcite 25 wt. % 600 5 1.88 86.1 81.2 76.5Synthetic Hydrotalcite 17.5 wt % 200 5 0.92 93.2 90.8 88.5 SyntheticHydrotalcite 17.5 wt % 400 5 1.57 88.4 84.3 80.4 Synthetic Hydrotalcite17.5 wt % 400 8 2.05 84.8 79.5 74.3 Synthetic Hydrotalcite 17.5 wt % 6008 3.02 77.6 69.8 62.2 Synthetic Hydrotalcite 17.5 wt % 600 8 2.87 78.771.3 64.1 Synthetic Hydrotalcite 17.5 wt % 600 5 2.21 83.6 77.9 72.3Synthetic Hydrotalcite, cooked 25 wt % 400 5 2.9 78.5 71 63.8 RehydratedSynthetic Hydrotalcite 200 5 14.62 N/A N/A N/A Reground 17.5 wt. %Rehydrated Synthetic Hydrotalcite 200 5 14.35 N/A N/A N/A Reground 17.5wt. % Rehydrated Synthetic Hydrotalcite Prill 400 5 13.75 N/A N/A N/A17.5 wt. % Rehydrated Synthetic Hydrotalcite Prill 200 5 14.9 N/A N/AN/A 17.5 wt. % Rehydrated Synthetic Hydrotalcite Prill 200 5 13.28 1.6N/A N/A 17.5 wt. % Hydrotalcite + phosphate 20 wt. % 200 5 11.29 16.4N/A N/A Hydrotalcite + phosphate 20 wt. % 200 5 12.32 8.7 N/A N/AHydrotalcite + phosphate 20 wt. % 400 5 11.99 11.2 N/A N/AHydroxyapatite 10 wt % 200 5 13.25 1.9 N/A N/A Hydroxyapatite 10 wt %200 5 13.13 2.8 N/A N/A Hydroxyapatite 15 wt. % 400 5 5.52 59.1 44.830.9 Hydroxyapatite 15 wt. % 600 5 9.38 30.5 6.2 N/A Hydroxyapatite 20wt. % 400 5 3.16 76.6 68.4 60.5 Hydroxyapatite 20 wt. % 600 5 3.8 71.862 52.5 Hydroxyapatite 25 wt. % 200 5 2.12 84.3 78.8 73.5 Hydroxyapatite25 wt. % 400 8 2.13 84.2 78.7 73.3 Hydroxyapatite 25 wt. % 600 5 2.6880.1 73.2 66.5 Hydroxyapatite 25 wt. % 700 5 2.82 79.1 71.8 64.7Hydroxyapatite 25 wt. % 700 5 2.43 82 75.7 69.6 Hydroxyapatite 25 wt. %600 8 0.24 98.2 97.6 97 Hydroxyapatite 25 wt. % 700 8 5.13 62 48.7 35.9Hydroxyapatite 25 wt. % 700 8 4.44 67.1 55.6 44.4

Example: Blast Test—Blast Suppression and Desensitization

The below table illustrates experimental results from blast testscompleted on various materials, in which stabilizer and combinations ofstabilizers and fillers were evaluated against a control SI baseline(ammonium nitrate). Materials evaluated for this blast test included:red lime (individually and in combination with bauxite residue atdifferent weight percentages), hydrocalumite (individually and incombination with bauxite residue at different weight percentages),hydroxyapatite (individually and in combination with bauxite residue atdifferent weight percentages), hydrotalcite (individually and incombination with bauxite residue at different weight percentages), acombination of hydrotalcite and hydroxyapatite (individually and incombination with bauxite residue at different weight percentages).

For this blast test, the hydrotalcite and hydroxyapatite were recoveredfrom an alumina production process. The standard operating procedure wasfollowed to prepare the blast components and complete the blast tests,while other variables were modified: i.e. the diameter of the tube (8″vs. 12″), the amount of booster (200 g, 400 g, 450 g), and the type offuel (i.e. fuel oil (FO), AL (aluminum)).

The specific impulse readings are provided below, along with acomparative view of the Reduction in Blast, measured as a percentageaccording to various SI baselines (e.g. 13.5, 10.0, and 8.0). When ablast test did not result in a reduction in specific impulse, thereduction percentage is indicated as “N/A”.

Reduction Reduction Reduction vs. 13.5 vs. 10.0 vs. 8.0 Booster Dia. Sp.Imp. Baseline Baseline Baseline Material (g) (in.) Fuel (kPa · ms/kg)(%) (%) (%) Ammonium Nitrate 450 12 AL 13.98 N/A N/A N/A Hydrocalumite20 wt % 450 12 AL 5.13 62.0 48.7 35.9 Hydrocalumite 20 wt. % 200 8 FO1.61 88.1 83.9 79.9 Hydrocalumite 20 wt. % 200 8 FO 1.99 85.2 80.1 75.1Hydrocalumite 20 wt. % 200 8 FO 1.34 90.1 86.6 83.3 Hydrocalumite 15 wt.% 200 8 FO 3.78 72.0 62.2 52.8 Hydrocalumite 15 wt. % 200 8 FO 4.17 69.158.3 47.9 Hydrocalumite 15 wt. % 400 8 FO 7.84 41.9 21.6  2.0Hydrocalumite 15 wt % + 450 12 FO 8.68 35.7 13.2 N/A bauxite residue 5wt % Hydrocalumite 2.5 wt. % + 450 12 AL 14.78 N/A N/A N/A bauxiteresidue 17.5 wt % Red Lime 20 wt. % 200 8 FO 3.68 72.7 63.2 53.9 RedLime 20 wt. % 200 8 FO 5.39 60.1 46.1 32.7 Red Lime 20 wt. % 400 8 FO12.45  7.8 N/A N/A Red Lime 15 wt. % 200 8 FO 15.21 N/A N/A N/A Red Lime15 wt. % 200 8 FO 13.40  0.7 N/A N/A Red Lime 15 wt. % + 200 8 FO 9.2131.8  7.9 N/A bauxite residue 5 wt % Red Lime 15 wt. % + 200 8 FO 5.2661.0 47.4 34.2 bauxite residue 5 wt % Red Lime 15 wt. % + 200 8 FO 4.6465.7 53.6 42.0 bauxite residue 5 wt % Hydroxyapatite 17.5 wt. % 200 8 AL6.21 54.0 37.9 22.3 Hydroxyapatite 15 wt % 200 8 AL 10.36 23.3 N/A N/AHydroxyapatite 12.5 wt % 200 8 FO 5.45 59.6 45.5 31.9 Hydroxyapatite12.5 wt % 200 8 FO 5.57 58.7 44.3 30.3 Hydroxyapatite 15 wt. % + 200 8AL 8.88 34.3 11.2 N/A bauxite residue 5 wt % Hydroxyapatite 15 wt. % +450 12 AL 8.63 36.1 13.7 N/A bauxite residue 5 wt. % Hydroxyapatite 10wt. % + 200 8 FO 4.17 69.1 58.3 47.8 bauxite residue 10 wt. %Hydroxyapatite 10 wt. % + 200 8 FO 5.34 60.5 46.6 33.3 bauxite residue10 wt. % Hydroxyapatite 10 wt. % + 200 8 FO 11.38 15.7 N/A N/A bauxiteresidue 10 wt. % Hydroxyapatite 10 wt. % + 200 8 FO 7.16 47.0 28.4 10.5bauxite residue 10 wt. % Hydroxyapatite 5 wt. % + 200 8 FO 4.82 64.351.8 39.8 bauxite residue 15 wt. % Hydroxyapatite 5 wt. % + 200 8 FO4.93 63.5 50.7 38.4 bauxite residue 15 wt. % Hydroxyapatite 2.5 wt % +200 8 FO 14.17 N/A N/A N/A bauxite residue 17.5 wt % Hydroxyapatite 2.5wt % + 200 8 FO 13.64 N/A N/A N/A bauxite residue 17.5 wt %Hydroxyapatite 2.5 wt % + 200 8 FO 4.59 66.0 54.1 42.7 bauxite residue17.5 wt % Hydrotalcite 17.5 wt. % + 200 8 AL 5.03 62.8 49.7 37.2 bauxiteresidue 2.5 wt. % Hydrotalcite 15 wt. % + 200 8 AL 8.86 34.3 11.4 N/Abauxite residue 5 wt. % Hydrotalcite 15 wt. % + 450 12 AL 12.31  8.8 N/AN/A bauxite residue 5 wt. % Hydrotalcite 10 wt. % + 200 8 FO 13.79 N/AN/A N/A bauxite residue 10 wt % Hydrotalcite 10 wt. % + 200 8 FO 4.4467.1 55.6 44.5 bauxite residue 10 wt % Hydrotalcite 10 wt. % + 200 8 FO13.45  0.4 N/A N/A bauxite residue 10 wt % Hydrotalcite 10 wt. %, 200 8FO 14.05 N/A N/A N/A bauxite residue 5 wt % Hydrotalcite 10 wt. % + 2008 FO 12.75  5.6 N/A N/A bauxite residue 5 wt. % Hydrotalcite 5 wt % +200 8 FO 5.86 56.6 41.4 26.8 bauxite residue 15 wt % Hydrotalcite 5 wt% + 200 8 FO 14.05 N/A N/A N/A bauxite residue 15 wt % Hydrotalcite 5 wt% + 200 8 FO 10.48 22.3 N/A N/A bauxite residue 15 wt % Hydrotalcite 2.5wt. % + 200 8 FO 15.18 N/A N/A N/A bauxite residue 17.5 wt %Hydrotalcite 2.5 wt. % + 200 8 FO 15.61 N/A N/A N/A bauxite residue 17.5wt % Hydrotalcite 2.5 wt. % + 200 8 FO 14.82 N/A N/A N/A bauxite residue17.5 wt % Hydrotalcite 10 wt. %, 200 8 AL 19.81 N/A N/A N/AHydroxyapatite 5 wt % Hydroxyapatite 10 wt. % + 450 12 AL 4.52 66.5 54.843.5 Hydrotalcite 5 wt % + bauxite residue 5 wt % Hydrotalcite 10 wt.% + 450 12 AL 7.84 42.0 21.6  2.1 hydroxyapatite 5 wt % + bauxiteresidue 5 wt. %

Example: Blast Test—Blast Suppression and Desensitization

The below table illustrates experimental results from blast testscompleted on various materials, in which stabilizer and combinations ofstabilizers and fillers were evaluated against a control SI baseline(ammonium nitrate). Materials evaluated for this blast test included:fire clay (individually and in combination with bauxite residue atdifferent weight percentages), hydroxyapatite (individually and incombination with bauxite residue at different weight percentages), andhydrotalcite (individually and in combination with bauxite residue atdifferent weight percentages).

It is noted that fire clay was utilized as a diluents (in lieu ofbauxite residue). The fire clay was obtained from a commercial vendor,and fire clay refers to a calcined commercial clay product that is aninert alumino-silicate material (e.g. applications in mortar/ceramicbricks, and refractory lining for furnaces and chimneys).

It is noted that EG AN refers to explosive grade ammonium nitrate, whichis a low density AN made for improved explosive performance (e.g. ascompared to the high density AN optimized for Fertilizer Grade FG.)

For this blast test, the hydrotalcite and hydroxyapatite were recoveredfrom an alumina production process. The standard operating procedure wasfollowed to prepare the blast components and complete the blast tests,though the diameter of the blast components was set at a standard 8″.Other variables were modified, including the amount of booster (200 g,400 g), and the type of fuel (i.e. fuel oil (FO), AL (aluminum), and PS(powdered sugar)).

The specific impulse readings are provided below, along with acomparative view of the Reduction in Blast, measured as a percentageaccording to various SI baselines (e.g. 13.5, 10.0, and 8.0). When ablast test did not result in a reduction in specific impulse, thereduction percentage is indicated as “N/A”.

Reduction Reduction Reduction vs. 13.5 vs. 10.0 vs. 8.0 Booster Sp. Imp.Baseline Baseline Baseline Material (g) Fuel (kPa · ms/kg) (%) (%) (%)Ammonium Nitrate (control) 200 PS 11.28 16.5 N/A N/A Ammonium Nitrate(control) 200 PS 11.06 18.0 N/A N/A Ammonium Nitrate (control) 200 AL15.39 N/A N/A N/A Fire Clay 25 wt % 200 FO 6.39 52.7 36.1 20.2 Fire Clay25 wt % 200 FO 11.17 17.2 N/A N/A Hydroxyapatite 17.5 wt % 200 FO 2.6680.3 73.4 66.8 Hydroxyapatite 17.5 wt % 200 FO 2.71 79.9 72.9 66.2Hydroxyapatite 17.5 wt. % 200 FO 4.70 65.2 53.0 41.2 Hydroxyapatite 17.5wt % 200 AL 4.97 63.2 50.3 37.8 Hydroxyapatite 15 wt. % 400 FO 5.97 55.840.3 25.4 Hydroxyapatite 15 wt. % 200 FO 4.69 65.2 53.1 41.4Hydroxyapatite 15 wt. % 200 FO 5.62 58.4 43.8 29.7 Hydroxyapatite 15 wt% 200 FO 12.94 4.1 N/A N/A Hydroxyapatite 15 wt % 200 AL 8.98 33.5 10.2N/A Hydroxyapatite 12.5 wt. % 400 FO 10.39 23.0 N/A N/A Hydroxyapatite12.5 wt. % 200 FO 4.87 64.0 51.3 39.2 Hydroxyapatite 12.5 wt. % 200 FO9.58 29.1  4.2 N/A Hydroxyapatite 12.5 wt. % 200 FO 1.95 85.6 80.5 75.7Hydroxyapatite 10 wt. % 200 FO 11.93 11.6 N/A N/A Hydroxyapatite 10 wt.% 200 FO 11.70 13.3 N/A N/A Hydroxyapatite 15 wt % + 200 PS 2.41 82.275.9 69.9 bauxite residue 2.5 wt % Hydroxyapatite 15 wt. % + 200 FO 4.3967.5 56.1 45.1 bauxite residue 5 wt. % Hydroxyapatite 15 wt. % + 200 FO2.13 84.2 78.7 73.4 bauxite residue 5 wt. % Hydroxyapatite 15 wt. % +200 FO 3.88 71.3 61.2 51.5 bauxite residue 5 wt. % Hydroxyapatite 12.5wt % + 200 FO 10.58 21.6 N/A N/A bauxite residue 2.5 wt % Hydroxyapatite12.5 wt. % + 200 FO 5.30 60.8 47.0 33.8 bauxite residue 2.5 wt %Hydroxyapatite 12.5 wt. % + 200 FO 4.11 69.6 58.9 48.6 bauxite residue2.5 wt % Hydroxyapatite 12.5 wt. % + 200 FO 3.33 75.3 66.7 58.4 bauxiteresidue 5 wt % Hydroxyapatite 12.5 wt. % + 200 FO 4.00 70.4 60.0 50.0bauxite residue 5 wt % Hydroxyapatite 12.5 wt. % + 400 FO 6.27 53.6 37.321.6 bauxite residue 7.5 wt % Hydroxyapatite 12.5 wt. % + 200 FO 3.9470.8 60.6 50.7 bauxite residue 7.5 wt. % Hydroxyapatite 12.5 wt. % + 200FO 3.75 72.2 62.5 53.2 bauxite residue 7.5 wt % Hydroxyapatite 10 wt.% + 400 FO 13.18 2.4 N/A N/A EG AN Hydroxyapatite 10 wt. % + 400 FO12.34 8.6 N/A N/A EG AN Hydrotalcite 26 wt % 200 AL 2.42 82.0 75.8 69.7Hydrotalcite 15 wt. % 200 FO 5.71 57.7 42.9 28.6 Hydrotalcite 12.5 wt. %200 FO 9.21 31.8  7.9 N/A Hydrotalcite 17.5 wt. % + 200 FO 1.68 87.583.2 79.0 bauxite residue 2.5 wt. % Hydrotalcite 17.5 wt. % + 200 FO1.01 92.5 89.9 87.4 bauxite residue 2.5 wt. % Hydrotalcite 17.5 wt. % +200 FO 1.21 91.0 87.9 84.8 bauxite residue 2.5 wt. % Hydrotalcite 17.5wt % + 200 AL 3.71 72.5 62.9 53.6 bauxite residue 2.5 wt % Hydrotalcite15 wt. % + 400 FO 2.78 79.4 72.2 65.2 bauxite residue 2.5 wt. %Hydrotalcite 15 wt. % + 400 FO 1.38 89.8 86.2 82.8 bauxite residue 2.5wt. % Hydrotalcite 15 wt. % + 200 FO 1.50 88.9 85.0 81.3 bauxite residue2.5 wt. % Hydrotalcite 15 wt. % + 200 FO 2.84 79.0 71.6 64.5 bauxiteresidue 2.5 wt % Hydrotalcite 15 wt. % + 200 FO 3.31 75.5 66.9 58.7bauxite residue 2.5 wt % Hydrotalcite 15 wt % + 200 FO 5.04 62.6 49.637.0 bauxite residue 2.5 wt % Hydrotalcite 15 wt. % + 200 FO 3.80 71.962.0 52.5 bauxite residue 5 wt % Hydrotalcite 15 wt. % + 200 FO 2.4781.7 75.3 69.2 bauxite residue 5 wt % Hydrotalcite 15 wt. % + 200 FO9.95 26.3  0.5 N/A bauxite residue 5 wt. % Hydrotalcite 15 wt % + 200 AL4.93 63.5 50.7 38.4 bauxite residue 5% hydrotalcite 15 wt % + 200 PS3.47 74.3 65.3 56.7 bauxite residue 5 wt % Hydrotalcite 12.5 wt % + 200FO 4.22 68.8 57.8 47.3 bauxite residue 2.5 wt % Hydrotalcite 12.5 wt % +400 FO 5.17 61.7 48.3 35.3 bauxite residue 2.5 wt % Hydrotalcite 12.5 wt% + 200 FO 8.55 36.7 14.5 N/A bauxite residue 2.5 wt % Hydrotalcite 12.5wt % + 200 FO 3.39 74.9 66.1 57.7 bauxite residue 5 wt % Hydrotalcite12.5 wt % + 200 FO 9.66 28.4  3.4 N/A bauxite residue 5 wt %hydrotalcite 12.5 wt % + 200 FO 3.71 72.5 62.9 53.7 bauxite residue 5 wt% Hydrotalcite 12.5 wt % + 400 FO 3.74 72.3 62.6 53.2 bauxite residue7.5 wt % Hydrotalcite 12.5 wt % + 200 FO 3.41 74.8 65.9 57.4 bauxiteresidue 7.5 wt % Hydrotalcite 12.5 wt. % + 200 FO 10.54 21.9 N/A N/Abauxite residue 7.5 wt. % Hydrotalcite 10 wt. % + 200 FO 12.84 4.9 N/AN/A bauxite residue 2.5 wt. % Hydrotalcite 10 wt. % + 200 FO 11.83 12.4N/A N/A bauxite residue 2.5 wt. % Hydrotalcite 10 wt. % + 400 FO 3.6373.1 63.7 54.6 bauxite residue 5 wt. % Hydrotalcite 10 wt. % + 200 FO3.78 72.0 62.2 52.8 bauxite residue 5 wt. % Hydrotalcite 10 wt. % + 200FO 10.26 24.0 N/A N/A bauxite residue 7.5 wt. % Hydrotalcite 10 wt. % +400 FO 10.07 25.4 N/A N/A bauxite residue 7.5 wt. % Hydrotalcite 10 wt.% + 200 FO 11.66 13.7 N/A N/A bauxite residue 10 wt. % Hydrotalcite 10wt. % + 200 FO 11.55 14.4 N/A N/A bauxite residue 10 wt. %

Example: Intercalation of Hydrotalcite

In order to intercalate hydrotalcites, the following procedure wasperformed, were anion substitution is completed by thermal activationfollowed by rehydration.

For thermal activation, 4.25 kg of HTC powder is placed in a ceramicbowl (to a depth of 1″) and heated to a temperature of 450° C. for onehour, followed by cooling below 100° C. in a furnace or in an externalholding unit (drying cabinet, desiccators).

For rehydration, approximately 12 L of water (DI or distilled) isstirred in a container, followed by phosphate addition (using diammoniumphosphate (DAP) add 1.6 kg (12 moles) to the 12 L of water) and mixuntil phosphate salt is dissolved (20-30 minutes). Slowly, activated HTCpowder was added and the resulting mixture is stirred for a minimum of12 hours. The wet slurry was placed in pans of ¾″ to 1″ depth and putinto a drying oven and dried at 125° C. until dry solids are obtained.The resulting intercalated HTC is screened to <20 mesh and stored foruse in the blast tests.

Example: Bauxite Residue Preparation as Stabilizer Material

In order to neutralize bauxite residue, phosphoric acid (85%) was addedto a BR slurry, while being mixed by an agitator. The pH of the bauxiteresidue was lowered to less than 8.0. The bauxite residue was permittedto settle and the resulting liquid was poured from the top of themixture and the resulting mixture was poured to ½ inch thick pans, andoven dried (100° C.). The resulting bauxite residue is believed to havea phosphate content of from 5 wt. % to not greater than about 10 wt. %based on the phosphoric acid neutralization.

Example: Preparation of Bauxite Samples

Raw Bauxite ore was reduced down to +/−20 mesh by feeding the orethrough a plate crusher, a roll crusher with serrated rolls (Sturtevantroll crusher), and a ball mill (with ceramic balls to further reduce theparticles to usable fractions. The resulting 20 mesh fraction wasblended with ammonium nitrate material and blast tests were conducted inaccordance with the above-referenced Example.

Example: Apatite Preparation from Bayer Liquor

Apatite tested in accordance with the aforementioned example was madewith precursor materials phosphoric acid, slaked lime and Bayer liquor,as per the following process. A mixture of phosphoric acid, carbondioxide, and refinery spent Bayer liquor was heated to 70° C. (In someembodiments, add additional carbonate or phosphate to increase yield. Insome embodiments, an alternative phosphorous source is crandalite.)Next, slaked lime was added and stirred for 15-30 minutes. The resultingmixture was filtered, washed and oven dried. After preparation,entrained liquor was removed via an additional filtration and washingstep.

The resulting material tested in accordance with the aforementionedExample had the following phases: carbonate hydroxyl apatite (major),hydroxyl apatite (trace), and possible trace quantities of CaCO₃ &hydrotalcite (e.g. formed via impurities in the slaked lime or formedduring the apatite production process).

The apaptite tested in accordance with aforementioned Examples is aBayer carbonate hydroxyapatite of the following formula(Ca₇Na₂(PO₄)₃(CO₃)₃(H₂O)₃OH) with major element as follows: 12-22 wt %CO₂; 44-49 wt. % CaO; 19-26 wt. % P₂O₅; 7-12 wt. % Na₂O; and 1-3 wt. %Al₂O₃.

Example: Methods for Making Fertilizer Composition

Ammonium nitrate is manufactured in three steps, including: (1)neutralizing nitric acid with ammonia to produce a concentratedsolution; (2) evaporating to provide a melt; and (3) processing byprilling or granulation to provide the commercial solid ammonium nitrateproduct. Prilling is the formation of a rounded, granular solid byallowing molten droplets to fall through a fluid cooling medium. In oneembodiment, prilling of AN involves spraying the concentrated solution(i.e. 96-99+%) solution into the top of a large tower. Then, thedescending droplets are cooled by an upward flow of air, solidifyinginto spherical prills that are collected at the bottom of the tower.

In one embodiment, fertilizer compositions of the instant disclosure aremade by spraying the concentrated AN solution (i.e. 96-99+%) whilesimultaneously spraying a concentrated solution of the stabilizermaterial(s) (e.g. suspended or in solution in a solvent) and co-prillingthe resulting fertilizer composition.

In one embodiment, fertilizer compositions of the instant disclosure aremade by adding the stabilizer material(s) to the concentrated ammoniumnitrate solution prior to prilling.

In one embodiment, fertilizer compositions of the instant disclosure aremade by coating the stabilizer material(s) onto the prill after the ANprill is formed. In some embodiments, a drum roller is used (e.g. withoptional solvents and/or binders) to adhere and/or coat the stabilizermaterial(s) onto the AN prill.

In some embodiments, the stabilizer material(s) are mixed into theammonium nitrate solution (with optional solvents) and the resultingfertilizer composition is recrystallized from solution or suspension.

In some embodiments, AN prills are ground with stabilizer material(s) ina milling press and utilized in a powder form. In some embodiments, thepowder is mixed with binder(s) and rolled into agglomerated forms. Insome embodiments, the blended powder is mixed with a binder and formed(e.g. pressed) into pellets or plates (e.g. with a disk-press orpelletization process).

In some embodiments, the solution (or suspension) of ammonium nitratewith stabilizer materials (e.g. optionally with solvents to reduceviscosity) are spray dried.

In some embodiments, the solution (or suspension) of ammonium nitratewith stabilizer material(s) is agglomerated (e.g. pan agglomeration),followed by a pelletization process.

Example: Method of Making Fertilizer

The following procedure was utilized to form ammonium nitrate coated inhydrotalcite. Subsequently, this coated fertilizer was utilized in thecrop studies (crop study #1).

As received ammonium nitrate fertilizer (AN) was added to an electriccement mixer, ceramic balls were added, and the AN was mixed for 2.5hours. The material was then screened to separate the AN (deagglomeratedAN) from the ceramic balls.

A composition of 80% ammonium nitrate: 20% hydrotalcite was screenedtogether to mix the materials, and processed in the ceramic mixer for 30minutes to blend the materials. The blended material was slowly added toa drum roller (pelletizing machine/fertilizer granulator), which wasoperated at a pre-set angle and speed, while binder (water) was slowlyadded in a fine mist to the blended mixture. As the water was added, theblended mixture formed pellets. In alternating fashion, blendedfertilizer material and water were sequentially added to the drum rollerand were formed into pellets. As the pellets rolled through the drumroller and increased in size and density, the pellets reached a suitableweight to roll out of the drum roller into a collection area.

Example Crop Studies

Two crop studies were completed utilizing fertilizer compositions inaccordance with one or more embodiments of the instant disclosure, inorder to evaluate how fertilizer compositions including stabilizermaterials performed in comparison to commercially available fertilizers.

Statistical analysis was performed on the crop yields, with the basicanalysis procedure as follows: test whether the variability differsacross the treatments; test whether the averages differ across thetreatments (e.g. using the appropriate method determined by whether (1)is true or false); and if at least two averages can be shown to bedifferent, identify which treatments differ. The statistical evaluationyielded that

The first crop study consisted of 1 fertilizer composition treatment(pelletized HTC with AN, (26-0-0)) and 5 Controls (no treatment (N/A),AN fertilizer (34-0-0), Urea fertilizer (46-0-0), UAN (liquid)fertilizer (30-0-0), and ESN fertilizer (44-0-0) (a commerciallyavailable polymer coated urea fertilizer)). Each treatment was appliedwith an equivalent Nitrogen delivery of 100 and 140 (lbs N/Acre). Tworesponses were measured: Ears/Acre, and Weight/Acre. In comparing thetwo responses, it was determined that there are no statisticallysignificant differences between the fertilizer composition (HTC+AN)compared to the commercially available fertilizer controls and nofertilizer addition. For the first crop study, there were no observabledifferences (in Ears/Acre or Weight/Acre) between the fertilizercomposition, nitrogen-bearing controls, or non-nitrogen control, norbetween low and high nitrogen levels of the same product.

The second crop study consisted of 3 fertilizer composition treatmentsand 5 Controls. Controls included: ammonium nitrate fertilizer, ureafertilizer, UAN fertilizer (liquid application), no fertilizerapplication, and ESN fertilizer (commercially available polymer coatedurea product). Three fertilizer compositions included: fertilizer #1: ANhaving by weight, 5% bauxite residue, and 15% hydrotalcite; fertilizer#2: AN having by weight, 5% bauxite residue and 15% apatite; andfertilizer #3: AN having by weight, 5% bauxite residue, 10%hydrotalcite, and 5% apatite. Each Treatment was applied with 120 LbsN/Acre and the Alcoa and AN Treatments were also applied at 261 LbsProduct/Acre. One response was measured: Yield @ 15.5% Moisture(Bushels/Acre).

In viewing the response, all products show higher yield (bushels/acre)than the non-nitrogen control. In completing the statistical analysis onthe response, it was determined that there are no statisticallysignificant differences between the fertilizer compositions compared tothe commercially available fertilizer controls and no fertilizeraddition (i.e. it is possible to distinguish some of the high Ntreatments from some of the low N treatments, but it is not possible todistinguish among the high N or among the low N treatments).

Various ones of the inventive aspects noted herein above may be combinedto yield fertilizer compositions and methods of making and using thesame to fertilize soil, while preventing, reducing, or eliminating thefertilizer (AN fertilizer) from being used in explosives and/orimprovised explosive devices.

While various embodiments of the instant disclosure have been describedin detail, it is apparent that modifications and adaptations of thoseembodiments will occur to those skilled in the art. However, it is to beexpressly understood that such modifications and adaptations are withinthe spirit and scope of the instant disclosure.

What is claimed is:
 1. A fertilizer composition, comprising: an ammoniumnitrate material; and an effective amount of a stabilizer material toresult in a specific impulse of not greater than 13.5 kPa*ms/kg whenmeasured in accordance with a blast propagation test; wherein thestabilizer material comprises an aluminum production byproduct, whereinthe stabilizer material is at least 12.5 wt. % of the total fertilizercomposition.
 2. The composition of claim 1, wherein the aluminumproduction byproduct comprises: a layered double hydroxide.
 3. Thecomposition of claim 1, wherein the stabilizer material compriseshydrocalumite.
 4. The composition of claim 1, wherein the stabilizermaterial comprises hydrotalcite.
 5. The composition of claim 1, whereinthe stabilizer material comprises hydroxyapatite.
 6. In someembodiments, the stabilizer material comprises an additive.
 7. Afertilizer composition, comprising: an ammonium nitrate material; and aneffective amount of a stabilizer material to result in a specificimpulse of not greater than 13.5 kPa*ms/kg when measured in accordancewith a blast propagation test; wherein the stabilizer material isselected from the group consisting of: layered double hydroxide,apatite, and combinations thereof; wherein the stabilizer material is atleast 12.5 wt. % of the total fertilizer composition.
 8. The fertilizerof claim 7, further comprising a filler material.
 9. The fertilizer ofclaim 8, wherein the filler material is selected from the groupconsisting of: bauxite residue, fire clay, red lime, and combinationsthereof.
 10. A fertilizer composition, comprising: an ammonium nitratematerial; and an effective amount of a stabilizer material to result ina specific impulse of not greater than 13.5 kPa*ms/kg when measured inaccordance with a blast propagation test; wherein the stabilizermaterial comprises hydrotalcite, wherein the stabilizer material is atleast 12.5 wt. % to not greater than 20 wt. % of the total fertilizercomposition.
 11. A fertilizer composition, comprising: an ammoniumnitrate material; and an effective amount of a stabilizer material toresult in a specific impulse of not greater than 13.5 kPa*ms/kg whenmeasured in accordance with a blast propagation test; wherein thestabilizer material comprises hydrotalcite, wherein the stabilizermaterial is at least 12.5 wt. % to not greater than 20 wt. % of thetotal fertilizer composition.
 12. A fertilizer composition, comprising:an ammonium nitrate material; and an effective amount of a stabilizermaterial to result in a specific impulse of not greater than 13.5kPa*ms/kg when measured in accordance with a blast propagation test;wherein the stabilizer material comprises hydrocalumite, wherein thestabilizer material is at least 12.5 wt. % to not greater than 20 wt. %of the total fertilizer composition.
 13. A fertilizer composition,comprising: an ammonium nitrate material; and an effective amount of astabilizer material to result in a specific impulse of not greater than13.5 kPa*ms/kg when measured in accordance with a blast propagationtest; wherein the stabilizer material comprises apatite, wherein thestabilizer material is at least 12.5 wt. % to not greater than 20 wt. %of the total fertilizer composition.